Hydrocarbon conversion and hydrocracking with layered complex metal silicate and chrysotile compositions

ABSTRACT

A NEW AND IMPROVED PROCESS FOR THE PREPARATION OF LAYERED COMPLEX METAL SILICATES, ESPECIALLY CHRYSOTILES, AT LOW SEVERITY CONDITIONS. THESE CRYSTALLINE FORM OF COMPLEX METAL SILICATE, FOR SHAPE RANGING FROM THICK WALL TUBES THROUGH THIN WALL TUBES, AND THIN WALL TUBES THROUGH FLAKES, CAN BE PRODUCED, WITH HIGH SURFACE AREA, AS DESIRED, IN HYDRATED FORM, BY CONTACT OF SUITABLE SILICA AND METAL SOURCES IN A REACTION OR SYNTHESIS MIXTURE AT PH OF AT LEAST ABOUT 10, AND PREFERABLY FROM ABOUT 12 TO 14, AT MODERATE TEMPERATURES AND PRESSURES. THE PROCESS CAN PRODUCE CHRYSOTILES, SOME OF WHICH HAVE BE FOUND TO EXIST IN NATURE, OR HETERFORE SYNTHETICALLY PRODUCED, BUT CAN AS WELL PRODUCE CHRYSOLITE SPECIES WHICH DIFFER CHEMICALLY OR PHYSICALLY, OR BOTH, FROM PREVIOUSLY KNOWN SPECIES. NEW AND NOVEL FORMS OF CHRYSOTILE ARE IMPROVED IN MANY OF THEIR PHYSICAL AND CHEMICAL CHARACTERISTICS AS CONTRASTED WITH PREVIOUS SPECIES, AND ARE PARTICULARLY USEFUL DIRECTLY OR INDIRECTLY IN CONDUCTING HYDROCARBON CONVERSION REACTIONS.

P 6, 1974 H. E. ROBSON HYDROCARBON CONVERSION AND HYDROORACKING WITH'LAYERED COMPLEX METAL SILICATE AND CHRYSOTILE COMPOSITIONS OriginalFiled Aug. 31 1970 CHRYSOTILE SYNTHESIS AT 250 6..

1.5 L75 2.0 (12.5) (l3) 03.5) N0 0 ISiOg O O 2 492 wofimam United StatesPatent ABSTRACT OF THE DISCLOSURE A new and improved process for thepreparation of layered complex metal silicates, especially chrysotiles,at low severity conditions. These crystalline forms of complex metalsilicate, for shape ranging from thick wall tubes through thin walltubes, and thin wall tubes through flakes, can be produced, with highsurface area, as desired, in hydrated form, by contact of suitablesilica and metal sources in a reaction or synthesis mixture at pH of atleast about 10, and preferably from about 12 to 14, at moderatetemperatures and pressures. The process can produce chrysotiles, some ofwhich have been found to exist in nature, or heterfore syntheticallyproduced, but can as Well produce chrysotile species which differchemically or physically, or both, from previously known species. Newand novel forms of chrysotile are improved in many of their physical andchemical characteristics as contrasted with previous species, and areparticularly useful directly or indirectly in conducting hydrocarbonconversion reactions.

This is a division of Ser. No. 68,324, filed Aug. 31, 1970 (now U.S.3,729,429, issued Apr. 24, 1973); and is related to application Ser. No.68,393, filed Aug. 31, 1970 (now U.S. 3,686,341, issued Aug. 22, 1972);Ser. No. 68,213, filed Aug. 31, 1970' (now U.S. 3,692,700); and Ser. No.68,394, filed Aug. 31, 1970 (now U.S. 3,686,348).

Certain forms of layered complex metal silicates are formed of sheets ofpaired layers of Si O or serpentine, fused together with layers of metalchemically combined with hydroxyl ions. Illustrative of such naturallyoccurring materials which have common morphological and structuralcharacteristics are chrysotile, Mg (OH) Si O garnierite, Ni (OH) Si- Ometahalloysite,

A1 (OH) Si O and kaolinite, Al (OH) Si O Synthetic complex metalsilicates of this character have been formed, these materials generallyretaining their high stability while having a higher degree ofdispersability, purity and homogeneity than those products found innature. These synthetic materials, particularly the pure materials, arethus useful as filtering mediums, absorbents, fillers and the like.Because of their high stability to heat, they are also useful in theproduction of high temperature or flame resistant fabrics, and can beused in woven and nonwoven fabrics.

Asbestos is a naturally-occurring complex metal silicate of thischaracter. The term, commonly used to identify a material of a fibroustextile nature capable of being woven into a fabric, is morespecifically used to identify a variety of serpentines calledchrysotile, ideally supra, a species of layered complex metal silicate.Though the structure can differ in chemical composition to some extentdue to the presence of impurities, this naturallyoccurring material asother forms of chrysotile is a serpentine of type formed of sheets ofpaired layers of Si O- fused together with layers of metal, in thisinstance mag- "ice nesium, chemically combined with hydroxyl ions.Investigations have been made of the properties of these forms ofcomplex metal silicates, and it has been reported, e.g., that naturalchrysotile has the configuration of hollow tubes or cylindrical fibrilswith an average outer diameter of 200 to 250 A. (angstrom units) and anaverage inner diameter of 20 to 50 A. As reported in the Encyclopedia ofChemical Technology, 2nd ed., vol. 2, p. 738 (Interscience Publishers),naturally-occurring chrysotiles typically have surface areas varyingfrom 4 to 12 square meters per gram (mF/g.) though by additionalfibrilization the surface areas can be increased to 30 to 50 mF/g. Nollet al. have reported [(Kolloid-Zeitschrift, vol. 157 [1], pp. 1 to 11)]that synthetic chrysotile,

can be prepared having areas ranging as high as mF/g. (BET Method). Nollet al. have also reported [Beitrage zur Mineralogie und Petrographie,vol. 7, 1960, pp. 232-241] synthetic nickel and cobalt substituted formsof chrysotile viz., garnierite, Ni (OH).,Si O and Co (0H) Si O withsurface areas ranging as high as mF/g. and mP/g. (BET Method),respectively. Little has been reported in regard to other forms ofchrysotile.

Chrysotiles have in the past been used as support materials, orcarriers, for oxidation catalysts such as platinum supported on naturalchrysotile for use in the conversion of sulfur dioxide to sulfurtrioxide. Despite the apparent advantage offered by the extremely highthermal stability of this class of complex metal silicate, thesematerials, insofar as is known, have never been used except as catalystsupports. A reason for this, perhaps, is because, in their naturalstate, little if any catalytic activity is shown. Moreover, though purerand more catalytically interesting forms have been preparedsynthetically over many years, these materials yet remain little morethan a matter of academic interest. Perhaps this is due in part to theextreme difiiculty of preparing even minute amounts of these materialsfor experimentation.

Until now, synthesis of layered complex metal silicates, highlypreferred of which are the chrysotiles, has only been possible underhydrothermal conditions at relatively high temperatures and extremepressures. Generally, temperatures on the order of 350 C. to 600 C., andhigher, and pressures on the order of 13,000 p.s.i. (pounds per squareinch absolute) to 23,000 p.s.i., and higher, have been employed toproduce these materials. Such extreme conditions, of course, are notconducive to commercial or large-scale operations, and though the purityand quality of these materials over the natural products have beenimproved some advantages, the properties nonetheless did not appear ofparticular interest for use of these materials as catalysts. In largepart, this is probably due to the relatively limited number ofinteresting specimens found in nature, the only major source of supply,to the low surface areas observed in the naturally-occurring forms ofthese materials, and to the only relatively modest gains made insynthesis even of the few of these materials which have beensynthetically produced.

Nonetheless, it is the primary objective of the present invention toobviate these and other prior art difiiculties.

A particular object is to provide anew and improved process forproduction of these layered complex metal silicates, or silicates formedof sheets of paired layers of Si O or serpentine, fused together withlayers of certain types of metal, or metals, chemically combined withhydroxyl ions.

A specific object is to provide such process which can be operated atlow severity conditions, i.e., at temperatures and pressuresconsiderably lower than heretofore possible, which process is capable ofproducing complex metal silicates resembling, or closely resembling, thechemical or physical composition, or both, of those found in nature aswell as a spectrum of new and novel complex metal silicates which differin chemical or physical composition, or both, from those found innature.

Another object is to provide complex metal silicate and chrysotilecompositions which differ in one or more of their chemical or physicalcharacteristics, or both, from those compositions found in nature, orheretobefore synthetically produced.

A further object is to provide complex metal silicates and chrysotileswhich differ in one or more of their chemical or physicalcharacteristics, or both, for direct or indirect use as catalysts, orcatalytic agents, for use in hydrocarbon conversion reactions.

In addition to the many known usages of the layered complex metalsilicates, supra, and the advantages offered by synthesis of thesematerials with greater adsorption and absorption capacities, and in highpurity state, the present compositions can be used directly or modifiedby known techniques for use in hydrocarbon conversion reactions forimproving the octane number of gasoline or converting relatively heavyhydrocarbons to light, lower boiling hydrocarbons, and includingconverting hydrocarbons by hydrogenation or dehydrogenation to saturateor unsaturate, in whole or in part, various species of molecularhydrocarbons. Among such hydrocarbon conversion processes arearomatization, isomerization, hydroisomerization, cracking,hydrocracking, polymerization, alkylation, dealkylation, hydrogenation,dehydrogenation, desulfurization, denitrogenation, and reforming.

It has now been found that layered complex metal silicates, particularlychrysotiles, of shape ranging from very thick wall tubes (substantiallyrods in character) through moderately thick wall tubes, thick wall tubesthrough thin wall tubes, and thin wall tubes through flakes can besynthetically prepared from soluble forms of silica, and certain metalsor their oxides and hydroxides in alkaline medium, in criticalconcentration, at moderate temperatures and pressures. The layeredcomplex metal silicates, including chrysotiles, formed in accordancewith the present inventive process, and certain of the high surface areacompositions of the present invention, are of crystalline structuredefined chemically by repeating units represented by the followingstructural formula:

where M and ii are selected from monovalent and multivalent metalcations, of valence ranging from 1 to 7, having an effective ionicradius [Goldschmidt radius, Effective Radii of Atoms and Ions FromCrystal Structure, p. 108, Langes Handbook of Chemistry, 10th ed.,Handbook Publishers, Inc., Sandusky, Ohio] ranging from about 0.5 toabout 1 A., and preferably from about 0.57 to about 0.91 A., x is anumber ranging from to 1, this number expressing the atomic fraction ofthe metals M and 1\ 1, a is the valence of M, b is the valence of M, nis a number equal in value to that defined by the ratio and w is anumber ranging from 0 to 4. Some species of these complex metalsilicates have been found to exist in nature, and some species have beensynthetically produced. Some species differ chemically from those foundin nature, or those heretofore synthetically produced, and others,though chemically similar, possess different physical properties.

Illustrative of this type of complex silicate, in any event, is the formof serpentine known as chrysotile, the dehydrated form of which has theidealized structural formula Mg (OH) Si O The formula is idealized inthe sense that chrysotiles, as other minerals, rarely, if ever,

appear in nature in pure form but contain very small amounts ofimpurities such as iron, aluminum, and the like, substituted formagnesium, and occasionally for silicon. Chrysotile is a mineral derivedfrom multiple layers of SL 0 or serpentine, condensed with Mg(OH) orbrucite layers, this material existing in nature as cylindrical shapedrods or thick tubes. The naturally-occurring mineral antigorite is alsoillustrative of such complex silicate having the idealized formula Mg(OH) Si O In nature, this material is also constituted of Si O orserpentine, condensed with layers of Mg(OH) or brucite. This material,however, is found in nature in the form of plates of undulating shape.Ortho serpentine, Mg (OH).,Si O a six-layer serpentine, is also found innature, as is lizardite, Mg (OH) Si O which is a one-layer serpentine.Both of these materials are found in the form of plates. Garnierite,anickel substituted form of layered complex silicate, Ni (OH) Si O isfound in nature in the form of tubes. Synthetic garnierite has also beenprepared by prior art workers, nickel having been substituted formagnesium in conventional synthetic chrysotile formulations. Cobaltchrysotile, Co (OH) Si O has been prepared in similar manner. Insofar asknown, however, attempts to prepare other useful forms of syntheticchrysotiles have failed.

The process of this invention can be employed not only to producecomplex metal silicates of known chemical composition, but also complexmetal silicates of new and novel chemical composition. It can also beused to produce both old and new chemical compositions with new,different, and unique physical properties, particularly as regards highsurface area compositions.

Chrysotiles of known chemical composition are thus included in theforegoing Formula I, but even these compositions can be produced withentirely different physical properties, especially as regards surfaceareas. Essentially pure forms of chrysotile, defined in the foregoingformula as those species wherein x does not exceed about 0.03 andpreferably about 0.01, are thus magnesium chrysotile, Mg (OH) Si O withsurface areas of above about m. /g., nickel chrysotile, Ni (OH)4Si Owith surface areas above about m. /g., and cobalt chrysotile, Co (OH) SiO with surface areas above about 190 m. /g., the maximum surface areasachieved by prior art practice, can thus be produced pursuant to thepractice of this invention. Other forms of chrysotile, included withinthe scope of this formula, can also be produced pursuant to thisinvention but with surface areas exceeding 110 m. /g., the maximumsurface area heretofore achieved by prior practice (exclusive of thenickel and cobalt chrysotile species). Preferred forms of these highsurface area species are those in the form of thin wall tubes of surfacearea ranging about mF/g. to about 250 m. /g., preferably about mP/g. toabout 200 m. /g., and those in the form of thin flakes of surface arearanging from about 250 m. g. to about 600 m. /g., and higher, preferablyfrom about 250 m. g. to about 450 mF/g.

Pursuant to the practice of the present process, compositions can beprepared which differ in their chemical structure from heretoforeexisting compositions in that they contain two or more metals insignificant concentration within the crystalline structure, and include,particularly, such compositions of high surface areas. These newcompositions are of crystalline structure defined by repeating unitsrepresented by the following structural formula:

wherein M and IT are metal cations having an effective ionic radius(Goldschmidt) ranging from about 0.5 to about 1 A., a expresses thevalence of M and is equal to 2, b expresses the valence of M and is aninteger ranging from 1 to 7, and preferably is an integer ranging from 2to 4, x is a number ranging from 0.01 to 0.50, preferably from 0.03 to0.20, and n is a number ranging from 2.5

to 3.3, and preferably from 2.7 to 3.0. w is a number ranging from to 4.Exemplary of such compounds are In these formulae, M and M can thus bethe same or dilferent metals, and these can be of the same or differentvalence. The complex metal silicates can thus contain essentially onemetal, or can contain two or more different metals in varyingconcentrations. In Formula I M and H can be monovalent or multivalentmetals of valence ranging from 1 to 7, while in Formula II M is adivalent metal. The valence of II can range from 1 to 7. II of theformulae can also represent more than one monovalent or multivalentmetal, though substantially bimetallic compositions are generallypreferred. The cationic form of the metal of the crystal must have aneffective ionic radius substantially within the ranges described.Illustrative of metals utilized in acceptable cationic form, which canbe selected from the Periodic Table of the Elements (E. H. Sargent &Company, copyright 1962 Dyna Slide Co.), are Group IA metals such aslithium, Group I-B metals such as copper, Group II-A metals such asmagnesium, Group II-B metals such as zinc, Group III-B metals such asscandium, Group III-A metals such as aluminum and gallium, Group IV-Bmetals such as titanium and zirconium, Group V-B metals such asvanadium, Group VI-B metals such as chromium, molybdenum and tungsten,Group VII-B metals such mauganese and Group VIII metals such as iron,cobalt, nickel, palladium and platinum.

Preferred metals from these classes are magnesium, nickel, cobalt,chromium, molybdenum, tungsten, palladiurn, platinum and aluminum.Magnesium is preferred be cause of the relative ease of formation of thecomplex magnesium silicates which are useful as catalysts, and suchsilicates are quite useful as support materials. Pursuant to the processof this invention, other complex metal silicates are formed bysubstitution of other metal ions for the magnesium. Nickel and cobaltare also preferred metals with known catalytic properties, and can bereadily substituted for magnesium, in whole or in part, to providehighly active hydrogenation components in formation of fuels processingcatalysts. Chromium is found highly suitable for formation of othercomplex metal silicates of the type herein described, and can be used toproduce aromatization catalysts of good quality for use in fuelsprocesses. Molybdenum is found useful, especially for the production ofhydrodesulfurization and reforming catalysts. Tungsten and palladium areuseful for formation of hydrocracking catalysts. Platinum is useful informing reforming catalysts and aluminum for use in the production ofcatalytic cracking catalysts. In general, the synthetic chrysotiles ofthis invention provide a means of maintaining a metal in dispersed formon a silica surface to provide greater activity, this being contrastedwith the addition of metals to such preformed support materials whichleaves something to be desired in maintaining this high state ofdispersion.

Complex metal silicates of these types can be synthetically prepared inhydrated form in very high yields from solution or gels, and thenconverted to dehydrated form by subjection to heat, as desired. Thecomplex metal silicates are prepared by reacting a metal cation sourcewith a silica source in proportions approximating the stoichiometriccomplex metal silicate composition, in an alkaline medium of pH rangingfrom about 10, and higher, and preferably at pH ranging from about 12 toabout 14, at moderate temperatures and pressures. Suitably, the reactionis conducted at temperatures ranging below 300 C., preferably attemperatures ranging from about 200 C. to about 275 C. Lowertemperatures can be used but the reaction proceeds quite slowly.Pressure in many systems are suitably autogenous, i.e., maintained atthe vapor pressure of the liquid solvent at the temperature ofoperation. This is especially true of aqueous mediums, these mediumsbeing especially preferred. Pressures as high as 12,000 p.s.i., andhigher, can be employed, but generally it is commercially unfeasible tooperate at pressures above about 1000 p.s.i. Preferably, pressuresranging from about 200 p.s.i. to about 1000 p.s.i., and more preferablypressures ranging from about 400 p.s.i. to about 800 p.s.i. aremaintained upon the reaction system. Reaction time ranges generally fromabout 0.5 to about 72 hours, and preferably from about 4 to about 24hours.

The compositions of the present invention encompass: (a) layered complexmetal silicates defined by Formula I where the surface area of thecomposition ranges above about m. /g., except as regards nickelchrysotile, Ni (OH) Si O and cobalt crysotile, Co (OH) Si O butencompasses these latter species wherein the surface areas range aboveabout m. /g. and mP/g. (BET Method), respectively; and (b) layeredcomplex metal silicates defined by Formula II, the higher surface areacompositions being especially preferred. The most preferred compositionsof the present invention, because they are admirably suitable for director indirect use as hydrocarbon conversion catalysts or catalystsupports, are the chrysotiles. For purposes of this invention,chrysotiles are those compositions defined in Formula I and Formula IIwherein the Si 0 or serpentine layers of the repeating unit which formthe crystals, are of smaller length or diameter than the associatedmetal hydroxide layers to which the serpentine layers are adjoined. Thischaracteristic structure is distinguishable from other layered complexmetal silicates, and other crystalline substances, by X-ray diffractionpatterns whether the crystal structures exist as tubes or flakes.

X-ray powder diffraction data for the two physically different forms ofchrysotile are as given below.

X-RAY DIFFRACTION PATTERNS FOR CHRYSOTILE Tubes: Flakes:

d (A.) I d (A.)-- I 7.50:.40 s. 4.50:.20 m. 4.55:.20 m. 3.67:.13 s.3.22:.10 w. 2.58:.06 m. 2.59:.06 m. 2.46:.06 m. 2.10-3.04 w. 1.7253025-w. 1.73:.025 w. 1.5253015- m. 1.542.015 m. 1.320:t.0l0 w. 1.311.010 w.

In obtaining the X-ray powder diffraction pattern, standard procedureswere employed. The radiation source was the K-alpha doublet for copper.A Geiger counter spectrometer with a strip chart pen recorder was usedin recording the data. The peak heights I, and the positions as afunction of 29, where 6 is the Bragg angle, were read from thespectrometer chart. From these, the relative intensities I wereobserved. Also, the interplanar spacing, d, in angstrom units,corresponding to the recorded lines, were determined by reference tostandard tables. In the above table, the more significant interplanarspacings, i.e., d values, for chrysotile tubes and flakes, respectively,are given. The relative intensities of the lines are expressed as s.(strong), In. (medium) and w. (weak).

In chrysotile it is thus known that the mineral is formed of .pairedserpentine and brucite layers which do not match, and hence the crystalis strained. Consequently, this gives rise to different physical formsand shapes inasmuch as relief from the strain is gained by a curl of thecrystal along its long axis so that chrysotile exists in nature ascylindrical shaped rods or thick wall tubes. The thick wall tubularstructure has been observed in synthetic forms of chrysotile. 'In thepresent process, the complex metal silicates are also formed as thickwall tubes, thin wall tubes, curls or flakes, as desired, from gels aspaired layers of different sizes. Layers of silicon-oxygen sheets arecombined with layers of hydroxyl groups cemented to the silicon-oxygensheets by metal cations. Each of the repeating units, considering forconvenience the anhydrous form, is thus formed of a layer of sepentine,or Si O and an adjacent larger sized layer of metal chemically combinedwith hydroxyl ions, or

to which the former is fused. The paired, fused metalhydroxyl ions andserpentine layers are held together by very strong forces of attraction,while the repeating units of paired layers per so are held together byweaker forces of attraction. A serpentine or Si O layer is formed of asheet of linked SiO, tetrahedra, three oxygen atoms of each SiO beingshared with adjacent SiO tetrahedra in the same layer. The vertices ofall the tetrahedra point in the same direction, or outwardly for a rodor tube structure. In the metal-hydroxyl layer or v layer, one-third ofthe oxygen atoms are oxygen ions which are shared with silica tetrahedraof the adjacent serpentine or SL 0 layer. The remaining oxygen atoms arehydroxyl groups, and these are associated only with M or M cations.Thus, the M or WI cations are surrounded by .six ions, four hydroxylgroups, or ions, and two oxygen ions in a case where the metal is adivalent cation such as magnesium.

These forms of layered complex metal silicates can thus be logicallyconsidered as chrysotiles, or substituted chrysotiles, since theypossess the chrysotile structure; and have been so characterized in theart in the forms known to existviz., as chrysotile, or magnesiumchrysotile, Mg (OH) Si O as nickel chrysotile. Ni (OH) Si O and ascobalt chrysotile, Co (OH) Si O Using the Pauling notation, a repeatingunit of the crystalline structure comprising five tiers of ions (1through 5) can be conveniently illustrated as follows:

Tier 1 is constituted entirely of oxygen ions. Tier 2, constituting thetetrahedral cation position, is essentially constituted of silicon ions.Tier 3 is constituted of both oxygen and hydroxyl ionsviz., two oxygenions and a hydroxyl ion. Tier 4, which constitutes the octahedral cationposition, is constituted of a monovalent or multivalent meal cation M orIT. This is the primary cation site for substitution of the variousmetals represented by M and K into the chrysotile structure. Where onlymagnesium is contained in the octahedral cation position, the chemicalstructureis that of chrysotile; and where nickel or cobalt is whollysubstituted for magnesium, the chemical structure is also thatheretofore produced synthetically and known as nickel chrysotile (orgarnierite) and cobalt chrysotile. Tier 5 is constituted entirely ofhydroxyl ions. The serpentine or Si O layer is constituted of thosetiers of ions ranging from 1 through 3, and the metal-hydroxyl ion layeris constituted of those tiers of ions ranging from 3 through 5. Two ofthe ions of tier 3 are shared between the serpentine layer and themetalhydroxyl ion layer, while the third ion is more identifiable withthe metal-hydroxyl ion layer. In the repeating unit tier 1 contains 3oxygen atoms, tier 2 contains 2 silicon atoms, tier 3 contains 2 oxygenatoms and 1 hydroxyl ion, tier 4 contains 3 magnesium ions and tier 5contains 3 hydroxyl ions. While it is not apparent from accepted Paulingnotation, the two layers are not of the same dimension, themetal-hydroxyl ion layer being of greater length than the serpentinelayer so that there is a misfit of the two layers, and hence a strainbetween the paired layers which form a repeating unit.

The metal-hydroxyl ion layer of a repeating unit is of greater area (andlength at least in one dimension) than an adjoining serpentine layer,the misfit between the two layers producing a stress-strain relationshipwhich causes the layers to curve in a direction such that the concaveside of the metal-hydroxyl ion layer adjoins the convex side of theserpentine layer. When the chrysotile is in tubular shape, this meansthat the structure is of coil shape, or formed of a series ofconcentric-like paired layers of the repeating units and the serpentinelayer is the smaller diameter member of the paired layers.

The misfit between the paired layers in conjunction with the pH of thereaction medium at the time the crystals are formed is believed to giverise, at least in part, to the present inventive process. Pursuant tothe practice of the present inventive process, in any event, it has beenfound that definite relationship exists between the pH of the alkalinemedium and the nature and physical form of the crystalline materialswhich are formed, as well as with respect to the temperature andpressure at which the reactions can be conducted. By conducting thereactions at a pH of above about 10, and preferably at from about 12 to14, it has been found that the reactions can be conducted atconsiderably lower temperatures and pressures than heretofore believedpossible. This not only makes large scale commercial operation feasiblebut, additionally, provides a means of product quality control. It hasthus been found that pH can be used to provide complex metal silicatesof the types described in physical forms and shapes ranging generallyfrom cylindrical shaped rods through thick wall tubes, from thick walltubes through thin wall tubes, and from thin wall tubes through flakes.On the one hand, where the chemical species is known to exist, some ofthe physical forms are found in nature, or have heretofore beensynthetically produced. Others differ physically from the natural forms,or forms heretofore synthetically produced. On the other hand, some ofthese materials are chemically as well as physically different forms.For example, chrysotile, Mg (OH) Si O is found in nature in the form ofrods and thick wall tubes of low surface area. This material has alsobeen heretofore produced synthetically as thick wall tubes with maximumsurface area of m. g. Thin wall tubes of higher surface areas areunknown. Other minerals having the same chemical structure as chrysotileare known to exist in nature, e.g., antigorite. It exists in nature asplatelets of undulating shape, and generally possesses a very lowsurface area. Garnierite, Ni (OH) Sl O and a cobalt form of chrysotile,Co (0H) 'Sl O have been synthetically produced, but as specimens ofsurface area ranging as high as mfi/g. and 190 m.'-/g., respectively.

A featureof this process is that by judicious selection of pH, surfaceareas can be improved considerably, generally at least two-fold andranging as high as almost ten-foldover the corresponding naturalproducts where they exist. The surface areas of these materials can thusbe controlled within conventional ranges, i.e., in the case of magnesiumchrysotile up to about 110 m. /g., or can be increased above 110 m. g.Preferably, tubes can be formed which have surface areas within therange of from about mfi/g. to about 250 m. /g., and higher, and morepreferably within the range of from about m. g. to about 200 mF/g.(B.E.T. method; absorption of N at its normal boiling point).Preferably, flakes can be formed with surface areas ranging from about250 m. g. to about 600 m. /g., and more preferably from about 250 m. g.to about 450 m. g. The nickel form of chrysotile, Ni (OH) Sl O and thecobalt form of chrysotile,

CO 4Si 05 in the form of tubes and flakes, can be produced with surfaceareas greater than 125 mF/g. and 190 m. /g., respectively, andpreferably within the higher range of limits described. It is found thatat different pH levels the character of the crystals can be controlledso that a given chemical specimen can be formed in the shape of rods,thick wall tubes, curls, or thin flakes and that surface areas can becontrolled during the transition, surface area increasing as pH islowered to favor, directionally, the production of rods through thickwall tubes, thick wall tubes through thin wall tubes, and thin walltubes through fiakes.

In general, in the formation of a species or chrysotiles at controlledconditions, as pH is lowered the tube walls get thinner, and the thinwall tubes generally yield surface areas no greater than about 200 m./g. to about 250 m?/ g. As pH is further lowered to obtain highersurface areas, the thin wall tubes form curls (or mal-formed tubes), andthen break apart and form higher surface area flakes, the walls ofwhich, directionally, also become thinner as pH is lowered. Thus, atconstant temperature and pressure, specimens of definite character areformed at a selected pH. The actual transition points vary to someextent dependent largely upon the nature of the metal, or metals, usedin formation of the complex metal silicate. The thickness of the wallsof the tubes can thus be directly controlled by the selected pH. I'hinwall tubes of only a few paired layers, e.g., 4 to 8 in thickness, canbe formed. Such tubes ranging from about 20 A. to about 70 A., andpreferably from about 28 A. to about 45 A., in thickness provide tubesof far greater inside diameter than occurs in the corresponding naturalproducts, providing far greater adsorption space and accessibility forcatalytic contact by reactant materials upon catalytic surfaces. Forexample, in sharp contrast to naturally-occurring magnesium chrysotilewhich exists in a cylindrical or rod-like form or in a thick walltubular form having an inner diameter ranging from about 20A. to 50 A.,high surface area chrysotile compositions of this invention exist astubes having inner diameters above 50 A., preferably from about 60 A. toabout 100 A., and higher. The accessibility and high concentration oflarge pore openings which exist in these materials are quite importantin considering the availability of surface areas for catalytic purposes.At surface areas above about 250 m./ g. the chrysotile compositions ofthis invention are usually formed as relatively thin flakes. The thinflakes, because of their ultra-high surface areas, are the mostpreferred compositions for use in most hydrocarbon conversion reactions.

As suggested, as the pH is further decreased, at the selectedconditions, the tubes begin to curl and then break apart to form thinflakes of very high surface area. The flakes range in thickness fromabout to 50 A., and preferably from about to 30 A.

It is feasible, at these low severity process conditions, to synthesizenew and novel complex metal silicates from solutions containing reactivesilicates, and reactive forms of the desired metal, e.g., soluble salts,or oxides and hydroxides. The reactants are combined in alkaline mediumat moderate temperature and pressure. The complex metal silicates areformed in two steps. In a first step, a synthesis gel is formed bycoprecipitation of the metal oxides or hydroxides with hydrous silicagel in alkaline medium. In a second step, the gel is heated at fromabout 200 C. to about 350 C., and preferably from about 250 C., to about275 C., so that the chrysotile product is crystallized from thesynthesis gel with rejection of excess water and soluble salts which areremoved by filtration and washing. At the time of formation of thesynthesis gel, the composition of the metal hydroxide layer of thecrystal is fixed by selecting the concentration of metals to vary theratios of M/M, as desired. The structures are useful as catalysts, orcan be further modified after initial formation, as desired, by cationexchange, as with ammonia and selected metal cations, or by impregnationwith metal anions or cations, or both, or by a combination of ionexchange and impregnation.

The process improvements whereby previously existing ornaturally-occurring complex metal silicates, as well as new and novelforms of complex metal silicates, can be made is effected by the use ofhighly alkaline mediums, of critical pH. High alkalinity causes thereaction to proceed at substantially milder conditions than heretoforebelieved possible. This favorable effect, which makes it generallyunnecessary to conduct the reactions at the higher conventionaltemperatures and pressures, is not completely understood. The highlyalkaline medium is employed to cause breakage of the silicon oxygenbonds, or depolymerization of the Si0 components, so that the latterbecomes more freely migratory within the solution or gel even atrelatively low temperatures and pressures. In any event, it is foundthat alkali concentration can be varied, as desired, in the reactionsystem to provide a variety of complex metal silicates, some resemblingproducts heretofore found in nature or produced by other synthesistechniques, either in their chemical or physical characteristics, orboth, and many products heretofore unknown as regards either theirchemical or physical characteristics, or both.

The nature of the reaction by virtue of which pH can be used to controlthe physical forms of the chrysotiles produced is thus not entirelyunderstood, but it would 'appear that the strain produced by the misfitof the unequal sized serpentine, Si O and the larger metalhydroxyl ionlayers is in part responsible for this phenomenon. Thus, at the selectedlow severity conditions, the strain is greatest on the layers farthestaway from the equilibrium diameter. At a given intermediate pH, crystalsassume the form of thin wall multilayer structures of only a few layersthickness. These crystals are of high surface area and possessrelatively large internal openings. At higher pH, the walls are thick,or the structure is even rod-like. At lower pH, the strain between thepaired layers causes the tube to break apart to form high surface area,thin flakes. The use, or substitution, of metal cations of differentsize into the octahedral cation position, which is believed to be theprimary cation site for substitutions, thus further alters thestress-strain relationship between the forming crystals. Hence, it wouldnot be expected that a single set of parameters could be used to definethe transition points, or zones, for the crystals of all of thedifferent metals which can be substituted at the primary cation sites.It is found generally, however, that cations which most closely approachin size the effective ionic radius of magnesium are most readilysubstituted, and in highest concentration. It also appears that the sizeof the larger metal hydroxide layer of a crystal structure is directlyrelated to the size of the cation substituted for magnesium and hencethe stressstrain relationship altered so as to effect the curvature ofthe structure caused by the misfit bet-ween the larger metal hydroxidelayer and the adjacent smaller serpentine layer. Whatever theexplanation, however, the technique is admirably suitable for producingwhole new families of high surface area crystals, and even families ofcrystals chemically different from those found in nature, or thoseheretofore synthetically produced.

Various alkaline materials can be used in the practice of thisinvention, providing they possess suflicient alkalinity to raise thereaction medium to the necessary pH, do not react to a significantextent with the forming complex metal silicates, with the intermediatematerials, precipitate the silica, or decompose to gaseous products.Most preferred of these alkaline materials, for these reasons, are thealkali metal and alkaline earth metal hydroxides, exemplary of which areGroup I-A metal hydroxides such as sodium hydroxide, potassiumhydroxide, cesium hydroxide and the like, and Group II-A metalhydroxides such as barium hydroxide, strontium hydroxide and the like. Asatisfactory Group III-A metal hydroxide is thallium hydroxide. Variousother materials such as tetra alkyl ammonium hydroxides, e.g., tetramethyl ammonium hydroxide, can be employed.

Various sources of silica can be employed in the present process, theseincluding essentially any of the conventional, widely used silicasources such as silica per se, diatomaceous earths, silica hydrogel,silica hydrosoi, alkali metal silicates, e.g., sodium silicate, and thelike. Particularly preferred sources of silicates are silica sol, silicagel, and sodium silicate olution (water glass).

Virtually any form of compound which is sufiiciently soluble andcompatible with the reaction mixture, which contains the desired metal,can be used as a source of the metal. Soluble salts of the metals, ormixtures of such salts, e.g., halides, sulfides, sulfates, nitrates,carbonates, acetates, phosphates, or the like, can be used to supply thedesired metal, or metals, in formation of the complex metal silicates.Exemplary of such salts are lithium chloride, lithium bromide, cupricchloride, cupric sulfate, magnesium chloride, magnesium bromide,magnesium sulfate, magnesium sulfide, zinc acetate, zinc chloride, zincbromide, scandium bromide, scandium sulfate, aluminum chloride, aluminumbromide, aluminum acetate, aluminum nitrate, aluminum phosphate,aluminum sulfate, gallium nitrate, gallium sulfate, titanium bromide,titanium trichloride, titanium tetrachloride, titanium oxydichloride,zirconium dibromide, zirconium sulfate, zirconyl bromide, vanadiumbromide, vanadium trichloride, vanadyl sulfate, chromic acetate, chromicchloride, chromic nitrate, chromic sulfate, molybdenum oxydibromide,tungsten trisulfide, manganous sulfate, ferric chloride, ferrouschloride, ferrous sulfate, cobaltous nitrate, cobaltous sulfate, nickelchloride, nickel bromide, palladium chloride, palladium sulfate,platinic tetrachloride, and the like. Many hydroxides, oxides, oroxygenated anions of these various metals can also be employed, andthese are particularly useful where it is desirable to increase the pHof the solution over and above that practical by a relatively weak base.Illustrative of such compounds are magnesium hydroxide, magnesium oxide,sodium tungstate, sodium unnecessary. Typically, the sources of silicaand metal are used in quantities sufiicient to provide a reactionmixture having a metal, or mixture of metals (calculated as the oxide oroxides), relative to the silica (calculated as the oxide) in mole ratioranging from about 1 to about 2, and preferably from about 1.4 to about1.6.

The invention will be more fully understood by reference to thefollowing data, selected to demonstrate the more salient features of thenovel process for preparation of these complex metal silicates, new andnovel compositions, and the process of their use in various hydrocarbonconversion reactions.

A first series of runs are presented to demonstrate the manner in whichpH can be used to control the production of the complex metal silicates.Chrysotile,

is first selected to illustrate complex metal silicates of chemical typewhich, though found in nature and heretofore synthetically produced, canbe nonetheless produced in new, different, and unique physical forms.

EXAMPLES 1-1 1 In each of the runs tabulated in Table I, the silicasource comprises either colloidal silica sol, 150 A. particle size, soldunder the Du Pont trade name as Ludox LS-30, or sodium metasilicate. Thesilica source is added to an aqueous solution of a suitable magnesiumsource, i.e., a magnesium salt, in concentration of parts by weight ofthe salt in 100 parts by weight of water. In order to produce thedesired pH, to a solution or gel is then added various amounts of analkali metal hydroxide, from a solution made up of parts by weight ofthe alkali metal hydroxide per parts by weight of water, with stirringfor about 5 minutes at 25 C. and atmospheric pressure. Typically, as isdemonstrated, the silica and magnesium sources are used in quantitiessufiicient to provide a reaction mixture having a MgO/SiO mole ratioranging from about 1.0 to about 2.0, but preferably of about 1.5. The pHof the solution ranges from 10 to 14, as determined by the amount ofalkali metal hydroxide added.

The resultant mixtures are placed, in separate series of runs, in anautoclave heated at 250 C. at pressure of 570 psi. After a period of 24hours, the resultant insoluble products obtained in high yield,substantially stoichiometric, are cooled, filtered, washed with tenvolumes of water to produce low sodium chloride levels, and dried at C.in an oven. All specimens are positively identified by X-ray diffractiondata as chrysotile.

TABLE I.BYNTHESIS OF CHRYSOTILE Reaction mixture compositions PhysicalSurface form of Silica Mg M 0/ Nero] H20] area, compo- Example sourcesource S0: SiOz S101 mJ/gJ sitions 1.5 2.5 42 72 Tubes.

1.5 1.0 51 468 Flakes.

1.5 1.0(K10/Sl07) 51 444 Do.

1.5 1.5 (KzO/SiOa) 51 467 D0.

1 Surface area, and all surface areas reported and claimed herein,determined by BET Method: N2 adsoprtion at its normal boiling of SurfaceArea by Nitrogen Adsorption,

point. Shell Development Company, Simplified Method for the RapidDetermination Report N o. S-98l5R, May 3 1945. l Colloidal silica 501A.) particle size sold under the trade name "Ludox LS-30.

I Reaction temperature of 275 Reaction at 275 C. for 48 hours. KOH usedas the alkali metal hydroxide.

molybdate, sodium chromate, sodium vanadate and the A definiterelationship is thus found to exist between like. Other metal sourcescan also be employed, e.g.,chlo- 70 the pH, or caustic mole ratio, andthe surface area of the roplatinic acid, chloropalladous acid and thelike.

The relative amounts of the silica and metal sources are most easilydetermined by the stoichiometry of the desired product, though the useof exact stoichiometric chrysotile produced. These results, graphicallyshown by reference to the attached figure, show that exceptionally highchrysotile surface areas are produced when alkali metal hydroxide isused in limited quantity to produce a amounts of these materials in agiven reaction mixture is 7 reaction mixture having an alkali metaloxide-to-silica mole ratio below 1.75, this corresponding to a pH ofabout 13.

Referring further to the figure, it is found that long tubular shapedcrystals with thick walls, openings of relatively small diameter, andlow surface area are produced at Na O/SiO ratios ranging from about 2.5to about 2.0. The wall thickness of such crystals thus ranges from about100 to about 50 A., the internal diameter of the openings from about 30to about 60 A., and the surface area from about 70 to about 120 m. g. AtNa O/SiO ratios between about 2.0 and 1.5, thin wall tubes with internalopenings of relatively large diameters and high surface areas areformed. The wall thicknesses of these types of tubes thus range fromabout 50 to about 30 A., the internal diameter of the tubes from about60 to about 150 A., and the surface area from about 120 to about 250m."-/g. Within the range of NagO/SiO ratios beginning at about 1.5, thethin wall tubes apparently break down to form porous flakes. Thus, at NaO/SiO ratios ranging about 1.5 and lower, thin flakes are formed. Suchflakes range in thickness from about 30 to about 20 A., and have surfaceareas which range from about 250 to about 600 m. /g., and higher.

These data show that pH can be controlled to ameliorate processconditions, as well as to optimize the quality of the products. Theprocess also makes it feasible to produce complex mixed metal silicates,as demonstrated by the following selected data.

EXAMPLE 12 A cobalt substituted chrysotile is prepared in the followingmanner: 50 parts by weight of Ludox LS-30 (described above) is addedwith stirring to a solution containing 9 parts by weight of CoCl -6-H O,68. 6 parts by weight of MgCl -6H O and 150 parts by weight of water. Asolution consisting of 30 parts by weight of NaOH and 50 parts by weightof water is then added to the aforedescribed mixture and stirred at 25C. and atmospheric pressure for about minutes. The resulting mixture isthen placed in an autoclave and heated to 250 C. for about 24 hours. Theproduct is then cooled, washed and dried using the procedure given withreference to the foregoing examples. The product recovered, which is inthe physical form of tubes, is a substituted chrysotile (identified byX-ray diffraction) having about 10% of the magnesium cations replacedwith cobalt cations and having a surface area of about 267 mfi/g.

EXAMPLES 13-21 The following series of data, given in Table II, isillustrative of additional runs for the preparation of substitutedmixed-metal forms of chrysotiles. All specimens are positivelyidentified by X-ray diffraction data as chrysotile.

example, Nesterchuk et al. (Zap Uses Mineralog Obshchestria 95 [1], 75-9[1966] and Roy et al. (American Mineralogist 39, 957, 975 [1954] havereported the synthesis of chrysotile at temperatures ranging from about350 to 600 C., at conventional hydrothermal conditions requiring apressure ranging from about 13,000 p.s.i. to about 23,000 p.s.i. Incontrast, production of chrysotile at 250 C, as described in theforegoing Example 12, requires pressures of only about 570 p.s.i. (vaporpressure of water at 250 (3.), and will readily permit the large-smilemanufacture of such chrysotiles.

i IAROMATIZATION Certain of the complex metal silicates can be used perse as catalysts, or can be composited with various materials to formcatalysts useful in aromatization of olefinic hydrocarbons, whetherstraight chain or branched chain, monoolefinic or polyolefinic andwhether conjugated or unconjugated. For example, straight chain olefinscan be converted to aromatic compounds, e.g., as in the conversion ofhexene-l and heptene-l to benzene and toluene, respectively. While suchprocess can be used for the conversion of olefins to aromatics forchemical uses, it is particularly important in petroleum fuelsprocessing. This is so in that olefins have many undesirable propertiesin motor gasoline and can be converted to aromatics with higher octanenumber to produce superior gasoline, while simultaneously eliminatingmaterials which contribute to gum formation and air pollution. Inaccordance with the present invention, however, higher octane numberproducts can be obtained and substantial portions of the olefiniccontent of feeds converted into desirable aromatics, without significantconversion to lighter hydrocarbons.

Olefinic hydrocarbons containing from about 6- to about 12 carbon atomsare preferred, and these are aromatized according to the presentinvention by contacting a suitable feedstock with the catalyst at lowpressures ranging, i.e., from about atmospheric to about 150 p.s.i., andpreferably at from about atmospheric pressure to about 75 p.s.i. Aninert gas, e.g., nitrogen, helium, methane, or the like, or hydrogen canbe employed. Use of an inert gas offers certain advantages inasmuch astheir use forces the reaction to proceed to completion whereas hydrogenis a product of aromatization. However, in certain cases, catalystdeactivation may occur and use of a moderate hydrogen pressure is quitebeneficial to prevent catalyst activity decline. Temperatures rangingfrom about 300 C. to about 800 C., and preferably from about 450 C. toabout 600 C., are used. High conversion of olefinic hydrocarbons withgood selectivity to aromatics are obtained.

In preparation of preferred types of aromatization catalysts atransition metal, or mixture of such metals, is gen- TABLEII.SUBSTITUTED CHRYSOTILES Reaction mixture composition 1 Reaction Totalcon- Percent of Mg Metal met dltions Surface replaced with cation Mgcation] NazO/ H20] hours at area, Physical form Ex metal cation sourcesource 81 1 S102 S102 250 C. MJ/g. of compositions 13; 20% Ni NiSO,MgSO; 1, 5 1.5 58 16 260 Curls and flakes. 14 100% Ni (garnierite)-NiSOi 1. 5 1. 25 58 24 338 Flakes. 15.--. 20% Co 00012611 0 MgCl, 1.52.5 52 p 24 122 Tubes. 16---- 10% Co COC1z-6H20, MgCl, 1.5 1.25 63 24403 Flakes. 17- 10% Fe F6012-6Hz0 MgCh 1.5 1.5 52 24 398 Do. 18. 10% Mn-MnClz-4H2O Mgclq 1.5 2.5 52 66 88 Tubes. 19---. 10% Cu. CuC1z-2HzO MgCla1.5 1.5 47 24 311 Flakes. 20. 10% Cr- CrC1a-6H O MgCl: 1. 5 2. 5 52 356Do. 21. 10% Zn Zn lg MgCl, 1.5 2. 5 47 24 166 Tubes.

1 Molar basis.

The present low severity process makes it quite feasible to produceconventional materials, or entirely new materials-viz, materials whichare different chemically or physically, or bothof wide variety suitableas supports or catalysts, or both, on a scale heretofore unknown. Theproduction of chrysotiles is thus now possible at temperaerallycomposited with a suitable base, as by impregnation of the base orcrystallization of the base with a suitable metal hydroxide. Thepreferred transition metals which are dispersed upon a suitable base areGroup VIII metals, illustrative of which is platinum, iridium,palladium, rhodium and including iron, cobalt and nickel. Group I-Btures significantly below those employed heretofore. For metals,preferably as their oxide, such as copper, silver and gold, can also becomposited with the Group VIII metals. Other metals, preferably in theform of their oxides, can be impregnated or otherwise composited, eitheralone or in combination with the Group VIII metals as, e.g., Group VI-Bmetal oxides such as chromium, molybdenum and tungsten. Preferredcomplex metal silicate bases are those chrysotiles formed in whole or inpart of magnesium or aluminum, or both. Illustrative of such bases arethin wall tubes and flakes of Preferably, the surface area of thetubular shapes range from about 110 mF/g. to about 250 m. /g., andflakes range preferably from about 250 mF/g. to about 500 m. g. andhigher. Preferred materials of these types also are chrysotilescontaining from about 2 to about 10 weight percent aluminum, and acorresponding amount of magnesium as described by Formula II.

Preferred chrysotiles useful per se as aromatization catalysts are thosehigh surface area forms of thin wall tubes and flakes containing,besides magnesium, about 0.1 to 1 weight percent platinum, or from about1 to 15 weight percent chromium oxide (Cr O or from about 1 to 15 weightpercent molybdenum oxide (M or from about 1 to 15 weight percenttungsten, as the oxide.

EXAMPLES 22-23 To illustrate useful catalysts for aromatization, aseries of selected data are set out below. In one instance, chromia iscomposited with magnesium chrysotile and, in another, platinum iscomposited with magnesium chrysotile to form aromatization catalysts.The chrysotile employed in each instance consists of flakes of 356 m./g., positively identified by X-ray diffraction data.

The chromia-magnesium chrysotile catalyst is prepared by dissolvingchromium oxide in water to form an aqueous solution, and then addingsame to the powdered magnesium chrysotile in amount sufficient to formpaste. The wetted powder is stirred to form a paste, the pastecontaining 15 weight percent chromium oxide on magnesium chrysotile. Thepaste is then heated in an oven at 150 C. for 16 hours. The dry mass isthen taken from the oven and crushed to a powder, and then calcined inair at 538 C. for 16 hours.

A portion of the catalyst composite is placed, as a fixed bed, in anupfiow reactor and contacted at reaction conditions, as specified below,with a 5095 C. cut of catalytic naphtha feed.

Feed composition, process conditions and the composition of the efiiuentare tabulated below.

TABLE III Process conditions:

Temperature, C.5l0 Pressure, p.s.i.g.- Gas-N 2 V./v./hr.-1

Liquid Feed product composicomposition, wt. tion, wt. percent percentAlkylbenzenes- 4. 02 5. 83 Polycyclles 0. 27 0. 38 Isoparaffins 39. 4(1) 38. 42

In another demonstration, a 0.3 percent platinum-onmagnesium chrysotilecatalyst is prepared by forming a paste by admixing the magnesiumchrysotile with an aqueous solution of chloroplatinic acid, drying samein an oven at 150 C. for 16 hours. The material is calcined at 1000 F.in air for 16 hours.

A portion of the catalyst composite is placed, as a fixed bed, in anupfiow reactor and reduced in 1 atmosphere of H at 1000 F. Thetemperature is then lowered to 950 F. and the gas switched to N Thecatalyst is then contacted with a 50-95" C. cut of a cat naphtha feed.

Feed composition, process conditions and the composition of the efiluentare tabulated below.

TABLE IV Process conditions:

Temperature, C.-510 Pressure, p.s.i.g.10

From these data it is observed that the concentration of aromaticsincreases from 4.02 percent in the feed to 7.70 percent in the product,an increase of approximately percent.

ISOMERIZATION The complex metal silicates can be used as catalysts orpromoters for isomerization reactions, 0r reactions wherein a feed whichcontains normal parafiins is converted to one which is enriched inisoparafiins. Notable among such isomerization reactions, and hence apreferred process, is that wherein hydrocarbon feeds orhydrocarboncontaining feed streams are treated to effect the conversionof normal C C C or C paraffins, or mixtures thereof, to their respectiveisomers for octane improvement. For example, n-butane can be convertedto iso-butane for subsequent alkylation to produce aviation gasoline.

The isomerization process is typically carried out at temperaturesranging from about 0 C. to about 450 C., and preferably within the rangeof from about 0 C. to about C. Operation at the lower temperaturesfavors the production of higher branched, e.g., the doubly branched,isomers which are of particularly high octane values. Space velocityshould range between about 1 v./ v./hr. to about 10 v./v./hr.,preferably between about 2 v./ v./hr. to about 5 v./v./hr. As spacevelocity is increased, the yield is decreased at a given temperature.Hydrogen may be employed in the reaction, but in any event the pressureat which the isomerization reaction is carried out should range fromabout 0 to about 1000 p.s.i., and preferably from about 0 to about 500p.s.i.

Typically, an active component such as aluminum halide is distended upona complex metal silicate or, alternatively, a complex metal silicatehaving a metal hydrogenation (or dehydrogenation) component. Preferredcomplex metal silicates are those species which are of low sodiumcontent and contain oxides of Group III-A metals, e.g., aluminum, andGroup VIII metals, e.g., cobalt, nickel, platinum, palladium, and thelike.

1 7 EXAMPLE 24 To demonstrate a typical low-temperature isomerizationreaction, a first run is conducted wherein aluminum bromide is distendedon a selected calcined form of chrysotile, (Mg (OH) Si O positivelyidentified by X-ray diffraction data. Thus, a hydrated magnesiumchrysotile in the physical form of thin wall tubes having an averagewall thickness of 30 A., an internal diameter of 120 A., and a surfacearea of 150 m. /g. is calcined in a furnace at 540 C. for 16 hours. Oneand sixty-eight hundredths parts by weight of the chrysotile is addedper 1 part by weight of aluminum bromide to a glass-lined reactionvessel, into which is also charged 5 parts by weight of n-hexane per 1part of aluminum bromide. The mixture is agitated for 4 hours at ambienttemperature and autogenous pressure. The reaction product mixture isthen neutralized with a solution of weight percent sodium hydroxidecharged into the vessel. The hydrocarbon layer is separated from thevessel and analyzed by gas chromatography.

For comparative purposes a second run is then conducted at identicalconditions except that unsupported aluminum bromide is employed in thereaction.

The composition of the various isomers in the total products and the Cisomer distribution in the two different products, in terms of weightpercent composition, are given as follows.

TABLE V First Second run- First run- Second total run-Cu total run-Ceprod. isomer prod. isomer compodistricompodistri- Isomers sition buttonsition button MP ethyl pentane. DMB =dimethyl butane.

In comparing these results, it is thus apparent that the chrysotile isquite effective as a promoter, especially for the production of the highoctane doubly branched isomers. Thus, in the set of data whereinchrysotile is employed as a promoter, 34.6 weight percent of 2,2- and2,3- dimethylbutane are obtained in the liquid reaction prodnet ascontrasted with only 6.2 weight percent of these doubly branched isomersin the run wherein the aluminum bromide is not promoted.

HY DROI'SOMERIZATION Hydroisomerization reactions can also be conductedwith the catalyst of this invention, the purpose of such process beingto convert feeds containing high concentrations of normal paraffins,particularly C and C n-paraffins, to products which have been enrichedin iso-paraflin content. In conducting such reactions, temperatures onthe order of from about 120 C. to about 260 C., and preferably fromabout 175 C. to about 230 C., and pressures on the order of from about150 p.s.i. to about 750 p.s.i., and preferably from about 200 p.s.i. toabout 500 p.s.i., are employed. Hydrogen is fed into the reaction at arate of from about 1000 to about 10,000 s.c.f./bbl. of feed, andpreferably from about 1000 to about 5000 s.c.f./ bbl. of feed. Whilespace velocity, LHSV, can range from about 0.5 to about 5, it preferablyranges from about 1 to about 2. In the reaction, the feed is normallycontacted with the catalyst while the former is in mixed phase-viz,liquid and gas. At constant contact time, the reaction appears favoredby lower pressures, and at lower reaction temperature the selectivity ofthe catalyst does not appear to be affected by total reaction pressure.The hydrogen-tohydrocarbon mole ratio should range from about 0.5 :1 toabout 10:1, and preferably from about 2:1 to about 5:1.

The preferred chrysotile catalysts are those of an acidic character. Forbest results, the chrysotile bases, e.g., magnesium chrysotile, nickelchrysotile, cobalt chrysotile, aluminum substituted forms of thesechrysotiles, or mixed metal modifications of these and other metals, aretreated with acidic agents such as hydrogen fluoride, aluminum chlorideand the like. Prior to such treatment, the acidic base is impregnatedwith a hydrogenation component viz., a metal, or metals, suitably aGroup VIII metal, preferably a noble metal such as platinum, palladium,or mixture of these and other metals. The metal is generally added inthe form of a salt and then reduced. Many times acidic agents such ashydrogen chloride or hydrogen bromide are added to the feed to maintaincatalytic activity.

EXAMPLE 25 For purpose of demonstrating such process, a 20% aluminumsubstituted form of magnesium chrysotile, in flake form with surfacearea of 350 m. /g., is synthesized, dewatered by centrifugation anddried at 50 C. The flakes are then slurried with a 10% aqueous solutionof ammonium nitrate, acetic acid is added to provide a pH of 3.5, andthe solution is then heated to 83 C. and this temperature maintained fortwo hours. The product, identified as the flake form of chrysotile byX-ray diffraction, is then filtered from the-solution and thenimpregnated with a solution of palladium tetra ammonium chloride, inconcentration sufficient to provide 0.5% palladium on the finishedcatalyst.

The catalyst is dried at C. for 16 hours in a vac uum, then ground to apowder, and fused into pellets. The pellets are then crushed to provideparticle sizes of 14-35 mesh (Tyler series). The pellets are thencalcined at 430 C. in a muffle furnace for 3 hours, cooled and a portionof the catalyst charged to a reactor.

Hydrogen is then cut into the reactor and the pellets reduced at 290 C.for 1 hour. The temperature of the reactor is thereafter lowered to 250C., and operated at atmospheric pressure. Hydrogen is purified to removeoxygen and water at 0 C., and is then passed through nhexane, saturated,and then fed into the reactor. The effluent from the reactor is analyzedby GO to determine the concentration of C iso-paraffins in the product.

1 Mol i-C (2-MP, 3-MP, 2,3-DMB, 2,2-DMB) Total mol C (i-C +n-C l (MPmethyl pentane) (DMB=dimethyl butane).

HYDROCRACKING These novel catalysts are suitable for use inhydrocracking at relatively low temperature and relatively high pressureto provide a process of considerable flexibility in changing the ratiosand character or quality of the products. Suitably, temperatures on theorder of from about 250 C. to about 450 C., and preferably from about350 C. to about 425 C., and pressures ranging from about 400 to about3000 p.s.i., and preferably from about 500 to about 2500 p.s.i., areused to convert middleboiling or high-boiling materials into high octanegasoline and jet fuel as well as for producing feedstocks for cat- 19alytic reforming. Space velocities, LHSV, can range from about 0.1 toabout but preferably range from about 1 to about 3, and hydrogen gasrecycle rates are generally maintained at from about 3000 to about12,000 s.c.f./bbl., and preferably from about 4000 to about 8000s.c.f./bbl.

The catalysts can be used as hydrocracking conditions in both sweet (lowsulfur) and sour (high sulfur) operations, or in the presence of bothsulfur and nitrogen. Conditions of temperature and feed, i.e., sulfurand nitrogen, can be adjusted to maximize yields of gasoline or jetfuel.

The several types of operation for which the catalysts of this inventionare useful can be illustrated in the now conventional process whereinthree reactors are employed in series, a first reactor of the seriesconstituting a hydrofiner, a second reactor of the series constituting afirst stage hydrocracker, and a third reactor of the series constitutinga second stage hydrocracker. In such operation, a catalyst is employedin the hydrofiner which is active in the presence of both organic sulfurand organic nitrogen and the conditions of operation are relativelymild. Cracking is held to a minimum, and both the sulfur and nitrogenare converted essentially to hydrogen sulfide and ammonia, respectively.Neither the hydrogen sulfide nor ammonia need be removed from theefiiuent passed from the hydrofiner to the first stage hydrocracker andhence the latter reactor is operated with sulfur and nitrogen present.The second stage hydrocracker of such reactor series can be operatedsweet, by removal of the hydrogen sulfide from the efiiuent of the firststage hydrocracker, or sour if desired, dependent upon the nature of thecatalyst employed. The catalysts of the present invention can be used ineach type of operation.

The wide range of products obtainable from this process is the result offorming complex metal silicates containing selective hydrogenationcomponents so that, in effect, dual-functional catalyst are produced.The cracking function is provided by the complex metal silicate and thehydrogenation function is provided by a metallic hydrogenationcomponent, e.g., Group VI-B, VII-B and VIII metals, of the PeriodicTable of the Elements, such as molybdenum, tungsten, platinum, nickel,cobalt and the like.

The hydrogenation component can be a metal, or mixture of metals, e.g.,a Group VIB, VII-B, or VIH metal, impregnated or otherwise depositedonto a chrysotile base or the hydrogenation component can beincorporated into the chrysotile structure at the time of synthesis, orboth. For example, preferred Group VIII noble metal components, e.g.,platinum or palladium, or mixtures of these and other metals, can bedeposited on a magnesium, nickel, or other type of chrysotile base, orchrysotile base containing a combination of magnesium, nickel, aluminum,platinum, palladium, and the like. Illustrative of preferred catalystswhich are useful in hydrocracking reactions are the mixed metalchrysotiles such as, e.g., magnesiumaluminum chrysotile impregnated bypalladium or platitwin, or both; magnesium-nickel chrysotile impregnatedby molybdenum or tungsten, or both; magnesium-tungsten chrysotileimpregnated by nickel or cobalt, or both, magnesium-molybdenumchrysotile impregnated by nickel or cobalt, or both; nickel-tungstenchrysotile; cobaltmolybdenum chrysotile, and the like.

Feedstocks which can be hydrocracked contain parafiins, olefins,naphthenes and aromatics. These materials are included in virgin orpreviously processed refinery streams boiling above about 200 C., andpreferably above about 235 C., e.g., light cat cycle oil boiling betweenabout ZOO-315 C., heavy cat cycle oil boiling between about 315-425 C.,light virgin gas oil boiling between about 200-315 C., and heavy virgingas oil boiling between about 315-540 C., and higher. Examples ofpreviously processed refinery streams include coker stocks, steamcracked stocks and cat cracker stocks.

20 EXAMPLES 26-37 To demonstrate the use of complex metal silicates ascatalysts, for these types of hydrocracking operations, portions offreshly synthesized chrysotiles, both in the physical form of tubes andflakes are centrifuged and dewatered, tray-dried at C. with circulatingair, positively identified by X-ray diffraction data, charged to an Ilermill and ground to a very fine powder. The initial physical form of thecomplex metal silicates, i.e., as tubes or flakes, is, of course,unaffected by milling.

The portions of powder are then exchanged with ammonium nitrate byadmixing with a 10 weight percent aqueous solution of ammonium nitratein water, the pH of which is lowered to 3.5 by addition of acetic acid.Contact between the solution and the powder is maintained for a periodof 2 hours, after which time the powder is dewatered by centrifugationand washed. This exchange procedure is twice repeated.

The portions of thrice exchanged material are then used per se, orimpregnated with a small concentration of metal, or metals, ashereinafter defined. Impregnation is acomplished by dissolvingsufiicient of a metal salt, or salts, e.g., palladium or platinumchloride, in aqueous hydrochloric acid or ammonia to provide the desiredmetal concentration and then the portions of exchanged material arecontacted with the solution and treated at a state of incipient wetness.The portions are then dried for 16 hours at 50 C. and then mixed withsufficient of an organic binder (Sterotex) to form a 2 percent by weightmixture of Sterotex and powder. The mixture is then pilled, crushed toparticles of 14-35 mesh size (Tyler series), and then calcined at 540 C.to burn out the binder. Upon cooling, portions of the catalyst arecharged to reactors and runs conducted in sweet and sour hydrocrackingoperations. In the sour hydrocracking operations, runs are made with andwithout added nitrogen.

After loading a reactor with catalyst, it is purged with nitrogen andthen pressured to 1500 p.s.i. with hydrogen at 370 C. for two hours. Thetemperature is then lowered to 215 C., feed is cut in and temperature isthen raised to obtain conversion of the feed to C -220 C. gasoline. Inthe runs, the space velocity, LHSV, is maintained at about 1, pressureis maintained at about 1500 p.s.i. and the hydrogen gas recycle rate atabout 7000-8000 s.c.f./bbl. Temperature is maintained at about 260 C.for sweet hydrocracking (second stage), at about 290 C. for sourhydrocracking (second stage) and at about) 365 C. for sour plus nitrogenhydrocracking (first stage The feed employed in the sweet hydrocrackingruns is a hydrofined light cat cycle oil containing very little sulfuror nitrogen. A similar type of feed, spiked with sulfur or both nitrogenand sulfur, is employed in the sour hydrocracking runs. In the sourhydrocracking runs simulating first stage hydrocracking operation, thefeed contains, by weight, 10,000 ppm. of sulfur (thiophene) and 1000ppm. of nitrogen (n-butylamine), and in the runs simulating sour secondstage hydrocracking operation, the feed contains 3000 ppm. sulfur(thiophene). For the runs simulating sour hydrocracking operations, thecatalysts are previously sulfided by passing a light cat cycle oil feedcontaining 3.2 weight percent sulfur over the catalysts for a period of16 hours at 260 C.

The results of these tests are tabulated below.

TABLE VIL-RUNS SIMULA'IING FIRST STAGE HYDRO CRACKING Sour: containssulfur plus nitrogen Surface area, mJ/g.-.

Physical form of base...

Conversion to 220 C. products,

percent.

21 22 "ar am nt-arse sitcom) STAGE HYDROCRACKING swa sow ExampleNo;..... 28 29'. '30 t. 31 32 33 34 35 36 37 rn stea 0.5%?0.-. 05% PkLQQ. 0.5% Pd-.;.-... .i.. 0.3% 1 0.5 Pd. w Ni w w. chrysotile base.--100% mg-. 8% Al, 100% Ni; 0.3% Pt, 0.3% Pt, 20% A1, 100% NL. 10% w N1,100% Ni. Temperature, 0. 31'- 072 M37 07% to Mg 03 4m 37% 322 372 M 375wig czar, 157 07 I so i V 28 I281 s92 80 217 "I: 100 3591 Plgsgggtorm..... Tubes..... Tubes Tubes"... Flakes Flakes Flakes Tubes.-.-Flakes Tubes Flakes. cglzlg elltlgltgg uu 23 n a7 so as 20 41 as 20.

ucts, percent. I

MLD-DISTHJLATE l5 powder. The portion of impregnated catalyst is driedfor For mid-distillate hydrocracking a .vir gin .or cracked 16 mixedwith suflidem aqua stock, e.g., cat cracker stock, steam cracker stockor coker solution of Sterotex a resldual of 2 oil, boiling above about3400 and ranging) about 5 weight percent of the Sterotex brnder 1n thecatalyst. The (3., and higher, containing both organicsulfur andorganicportion of catalyst then crushqd and plllid to 1445 nitrogen can beemployed. Vacuum or atmospheric gas mesh (Tyler and then calcmcd at 540to burn oils containing from about 1 to about 4 weight P rcent out thesiemtex bmder sulfur, and to about 2000. p.p.m. of nitrogen, can thus beA Porno of the catalxst upon coolmg 18 then charged processed toproduced high concentrations of middle distilto a reactor the reacforsealed i f' wlth 3 lates, relative to lower boiling cracked products. f.drogen 1500. Safanaya vu'gm gas The conditions employed formid-distillate hydr'ocrackmg'about Yvelght if Sulfur and of mtrofl ingare within the ranges described for hydrocracking, but 5" havmg boilingrange 340 0-540 and temperature are generally a littlehigherthamrquilied higher, 1s then cut into the reactor. To sulfide thecatalyst for more conventional hydrocracking. This is because the thereactor is 1n1t1ally maintained at a temperature of 335 catalystsemployed for mid-distillate hydrocracking' have after l days thecatalyft sulfided' t t lower acidity than conventional hydrocrackingcatalysts. Increased to 420 and mld-dlsnnate Typically, temperatures inmid-distillate hydrocracking Pydmmckulg coilducted In the the spacevelocranges fro about 370450 I, p L 1ty, LHSV, is maintained at about 1,hydrogen pressure The chrysotile catalyst is prepared so that it is ofinter- 1500 and hydrogen gas recycle rate at 20004 000 mediate acidityranging from about 0.2-to about 0.9, and s'QfJbbl' preferably from about0.2 to about 0.5 as measured by pyridine adsorption. Pursuant to thistechnique,'thc acidity is measured by placing the catalyst ona'microbalance and heating under vacuum at' 427 C. for one hour. Thetem' perature is then lowered to 260. C. and the catalyst-then subjectedto a pressure of two millimeters of pyridine.'Under these conditions thecatalyst takesup pyridine until equilibrium is reached. The amountofpyridine absorbed at these conditions measured in 'millimoles 'pergram of catalyst is taken as the measure of the acidityof the catalyst.I

The chrysotile catalyst can be'fiised in 'the' formof tubes or flakes,but tubular forms (pf-chrysotile are'generally preferred. Preferredforms aremaghesium chrysotile and nickel chrysotile. Nickel chrysotileis of particularly high activity and selectivity in conversion ofhydrocarbon feeds to mid-distillate liquid products, with high ratios ofmiddle distillates to lower boiling product's. Magnesium chrysotile with10-35 mole' percent of themagnesium substituted by aluminum is alsopreferred v I The catalysts are generally formed withi'the desiredconcentrations of metals, e.g., nickel, magnesium and aluminum, at thetime of synthesis. -Additional hydrogenation components are often addedto the catalyst composite.

Thus, it is often desirable to add another metal, or metals (or metalcompounds) to the composite, e.g., by impregnation. Groups VI-B, VIIBand Vlllm'etals, particularly cobalt and molybdenum, andmixtures-thereof have been found particularly useful in mid-distillatehydrocracking.

' EXAMPLE 38 To demonstrate mid-distillate.hydrocracking with catalystof this type, a selected species of chrysotile-is synthesized asidentified hereafter, a portion thereof 'dewatered by centrifugation,dried at, 180 C. in circulatingv air, identified by X-ray diffraction,ground to a'fine powder and then impregnated by the above-describedincipient wetness technique with a solution of ammonium molybdate.Sufiicient solutionis. used to provide, 12.5 weightpercent of the salt,calculated as molybdenum oxide,.iu.,thc

The results of this run are given in the table below.

. TABLE IX Example No.1: 39

'Impregnated metal: Mo

CRACKING The complex metal silicates can also be utilized as catalystsin cracking processes, or processes wherein decomposition of hydrocarbonis accomplished by contacting suitable hydrocarbon feeds with a catalystat elevated temperatures, The purposes of cracking is generally toproduce gasoline or heating oils from higher boiling hydrocarbonfractions, though specific gaseous hydrocarbons such as ethylene,propylene, butylene, isobutylene, or the like, can .be recovered, ifdesired. Suitable feedstocks for cracking are those boiling above about260 C., this including virgin or treated stocks and atmospheric or vac-.uum gas oils boiling up to about 600 C. At times, gasoline boilingrange materials, or residuum boiling above 600 C., are cracked.

When using these novel catalysts, catalytic cracking is carried outatsubstantially atmospheric pressure or at somewhat elevated pressure,e.g., up to about 50 p.s.i., and at temperatures ranging from about 400to about 650 C., and preferably from about 475 C. to about 550 C.,usually in fluid or moving catalyst beds. In once-through operation,about 30-60% conversion is usually obtained, and generally some of theunconverted material boiling above about 220 C. is recycled to increasegasoline yield.

Illustrative of preferred catalysts useful in catalytic crackingreactions are, e.g., magnesium chrysotile and miited metal modificationssuch as magnesium-aluminum chrysotile. To illustrate the use of complexmetal silicates generally for use in a catalytic cracking process, thefollowing selected dataare given.

23 EXAMPLE 39 To demonstrate the advantages of such composite catalysts,a portion of the basic chrysotile material (20 mole percent Al, 80 molepercent Mg flakes), as synthesized, is dewatered by centrifugation,dried at 180 C. in air, identified by X-ray diffraction, and then mixedor co-gelled, in weight proportions, with an amorphous catalyst (13%alumina and 87% silica) sufficient to provide 15% of the chrysotile inthe finished catalyst. Such gel is then spray dried to form 40-60 micronspherical particles.

A portion of the catalyst is charged to a fluid bed reactor. Steam isintroduced for two minutes to strip the catalyst and purge the reactorof air. A vaporized feed of East Texas light gas oil, boiling between340-455 C., is then passed over the catalyst for two minutes at areactor temperature of 510 C. The feed is introduced at suflicient spacevelocity to obtain 60 percent conversion. The higher boiling products ofthe reaction are condensed and collected while the uncondensed light gasis directly measured and analyzed by mass spectrometry. The condensedprod ucts are measured by gas chromatography. A sample of the catalystis removed to measure the carbon content.

Standard commercially used silica-alumina and zeolite cracking catalystsare run under identical conditions, and

the results of these runs compared as tabulated below.

TABLE X 20% alumina flakes (15% chrysotile- 85% silica- Zeolite alumina)NFNOI common EXAMPLE 40 A run is made, similar in all respects to thatmade pursuant to Example 39, except that essentially pure magnesiumchrysotile in flake form with surface area of 410 mF/g. is incorporatedwithin the silica alumina matrix. This catalyst is also quite active forcracking reactions.

EXAMPLES 41-44 The following illustrative data demonstrate the eflicacyof a magnesium chrysotile catalyst wherein certain molar concentrationsof the magnesium have been substituted or replaced by aluminum in thebasic chrysotile structure. n the one hand, as will be observed from thefollowing data,

sired concentration of aluminum metal relative to the concentration ofmagnesium. Ludox (or silica sol), and then a 10% or 35% replacement ofthe magnesium has little sodium hydroxide, is then added to the mixturesto gel the silica and precipitate the magnesium, alumina and silica.Crystallization is then accomplished by heating at 250 C. for 24 hours.The several portions of catalyst are then dewatered by centrifugation,dried at 180 C., identified by X-ray diffraction, powdered, pressed on ahydraulic ram, the compacted forms of catalyst then crushed to 14-35mesh (Tyler series), and then calcined at 540 C. for 16 hours. v

The portions of catalyst are then charged to reactors, and thetemperature adjusted to 280 C. A stream of helium is then passed througha saturator filled with cumene at 18 C. and then passed at 0.3 w./w./hr.into the reactor and contacted with the catalyst. The effluent from thereactor is then analyzed by gas chromatography to determine the amountof conversion of the cumene to benzene and propylene.

The results are tabulated below.

1 All catalysts are flakes. 1 W.'/hr./w.==-0.3; Temp.=280 C. 1 Firstorder rate constant for cumene cracking reaction.

HYDROGENATION (HYDROFINING) An important application of the complexmetal silicates of the present invention involves hydrogen saturation ofunsaturated hydrocarbons such as aromatics and olefins,including'monoolefins and polyolefins, whether straight chain orbranched chain, and whether substituted or unsubstituted. In fuelsprocessing the saturation of lower molecular weight olefins having acarbon content ranging from about 2 to about 12, and preferably fromabout 2 to about 6, is generally of greatest importance. For example,butylene polymers and light catalytically cracked naphtha, steam crackednaphtha, and the like, can be hydrogenated to produce aviation gasolinecomponents. In hydrogenation, hydrogen atoms are directly added tounsaturated bonds of the material being processed. Other importantapplications of hydrogenation of which the present catalysts aresuitable include refinement of lube oil distillates, production of highquality diesel oils, heating oils, and kerosene. The catalysts are alsosuitable for use in removal of organic nitrogen and sulfur to improvethe color andstability of various products, e.g., heating oils.

The preferred chrysotile catalysts are those forms of high surface'area, preferably flake forms ranging in surface area from about 250 m./'g. to about 500 m. /g., and higher. The catalyst used in suchreactions is preferably one of mild acidity, and while the hydrogenationcomponent can be incorporated into the chrysotile structure at the timeof its formation, by ion exchange or by impregnation, or depositedthereon as by impregnation, it has been found'that incorporation of thehydrogenation component into the structure provides better dispersion ofthe metal, or mixture of metals. Such catalyst is thus more stable,there is less tendency of the metals to agglomerate, and betterdispersion is maintained throughout the reaction. Activity maintenanceis generally superior.

Preferred metals for incorporation, or deposition, but preferably forincorporation ab initio within the chrysotile structure are those ofGroups VIB, VII-B and VIII of the Periodic Table of the Elements,including, e.g., chromium, cabolt, molybdenum, rhenium, cobalt, nickel,platinum, palladium, or mixtures of these and other metals.

Hydrogenation reactions are generally conducted at temperatures rangingfrom about 50 C. to about 450 C., preferably from about '150"G"to'about"350"C;, and at pressures ranging from about. 100 p.s.i. toabout 3000 p.s.i., preferably from about 200 p.s.i. to about 500 p.s.i.Space velocities, LHSV, generally range from about 0.5 to about 5, andpreferably from about 1 toabout 2. Hydrogen is generally introduced at arate of from about 300 to about 5000 s.c.f./bbl., and preferably fromabout 500 to about 3000 s.c.f./bbl.

EXAMPLES 45-47 To demonstrate the high activity of chrysotiles ashydrogenation catalysts, a series of selected data are set out below.The data show a series of runs wherein nickel chrysotile flakes per seare used as a catalyst for hydrogenation of benzene. A comparative run'is also described using similar nickel chrysotile flakes, to whichtungsten has been added. A third run is also described wherein 20 molepercent aluminum substituted magnesium chrysotile flakes is employed, towhich palladium has been additionally added by impregnation. Thesecatalysts are prepared and identified in the same manner as those usedand previously described as hydrocracking catalysts. All of these runsare compared with a conventional commercial platinum-on-aluminacatalyst, consisting of purchased yi -inch extrudates crushed to 14-35mesh (Tyler series). I

In the runs, the catalysts are charged to the reactors and pretreatedwith hydrogen at 370 C. for 16 hours to assure complete reduction of thecatalyst. This flow is then terminated. Hydrogen is then passed throughbenzene at 18 C. to saturate the hydrogen stream, and

the stream is then passed into the respective reactor at the temperatureindicated, and at a rate of 1 w./hr./w.' The pressure is maintained atatmospheric. The eflluent from the individual reactors is analyzed bygas chromatography to determine the amount of conversion ofbenzene' to"cyclohexane. v

The results are tabulated below.

TABLE XII Catalyst:

Impregnated metal 10% W. 0.5% Pd.-. 0.6% Pt. Base 100% N1... 100% Ni.-.20% AL--- A1203. Temperature, C 80 235 51 Conversion to cyclo- 29 45 2956:

hexane, percent.

k (hrs.- .35...-- 0.62".-." 0.34""-.- 0.81. Base, surface area, 359 392359 rn. lg. Physical form of Flakes.-.. Flakes Flakes...- chrysotile.

I First order rate constant for benzene hydrogenation.

These data clearly show that these catalysts possess very goodhydrogenation activity, this being true not only of chrysotiles whereinthe hydrogenation component is deposited or impregnated into thestructure, but also for chrysotiles wherein the hydrogenation componentis incorporated ab initio into the structure.

HYDRODESULFURIZATION The catalysts of this invention are particularlyappli-:=

in residuals, which normally poison and deactivate hydrodesulfurizationcatalysts. Indirect hydrodesulfurization of feedstocks can also beaccomplished by distilling out gas oil fractions from a heavierresidual, treating the gas oil to remove sulfur, and then blending thedesulfurized gas oil with the untreated residuum. The composite product,of course, contains less sulfur than.prior to such treating andblending. Typically, e.g., a fuel oil containing 2-3 percent by weightsulfur can thus be treated to meet specifications requiring a maximumsulfur content of 0.5 percent by Weight sulfur.

In direct treatment of hydrocarbon feedstocks, e.g., in a fixed bed orebulluting bed, it is generally preferred to operate, at the start ofthe run, at temperatures of about 340 C. to about 390 C., and attemperatures ranging from about 390 C. to about 490 C. at end-of-runconditions. The pressures employed usually range from about 300 p.s.i.to about 3000 p.s.i., and preferably from about 800 p.s.i. to about 1500p.s.i. Hydrogen rates range generally from about 500 s.c.f./bbl. toabout 10,000 s.c.f./ bbl., and preferably about 1000 s.c.f./bbl. toabout 5000 s.c.fJbbl. The liquid hourly space velocities, LHSV, rangegenerally from about 0.1 to about 10, and preferably from about 1 toabout 3. The conditions employed for indirect dehydrosulfurization aregenerally similar except the temperature employed is about 50 centigradedegrees less at either start-of-run or at end-of-run conditions.

The hydrodesulfurization catalyst is generally comprised of a compositewhich includes a chrysotile base and a hydrogenation component, viz., ametal, a metal oxide, or a metal sulfide, wherein the metal is fromGroups VI-B, VIII, or both, of the Periodic Table of the Elements. Theconcentration of the metal, or mixture of metals incorporated within thechrysotile base can vary widely, dependent on the nature of thehydrogenation component and feedstock. The metal, or mixture of metals,of which cobalt, molybdenum, tungsten, and nickel are preferred, isgenerally incorporated within the base in concentration ranging fromabout 0.1 to about 25 percent by weight, and preferably from about 0.3to about 15 percent by weight, of the total composite. Whenhydrogenation components such as the oxides or sulfides of cobalt andmolybdenum are utilized, the concentration will be generally 1 to 5percent and 5 to 15 percent, respectively, based on the total weight ofthe composite. The chrysotile base, e.g., magnesium chrysotile, nickelchrysotile, or either, wherein the magnesium or nickel is substituted inpart by aluminum, is preferably one of pore size ranging between about30 A. and 120A. diameter. Tubes of pore size ranging between about 70 A.and A. diameter, and flakes ranging between about 30 A. and 80 A.diameter, particularly the former, are most preferred. Chrysotiles ofsuch pore sizes are readily formed and pore sizes readily controlled,within close limits, pursuant to the present inventive process.

To demonstrate the present process, a series of data is selected and setforth below.

EXAMPLES 48-53 A series of catalysts, as described hereafter, issynthesized, dewatered, dried, identified by X-ray diffraction, groundto a fine powder and impregnated by incipient wetness technique. Thecatalysts are then dried, admixed with an organic binder, pilled,crushed to 14-35 mesh (Tyler series) and calcined to burn out theorganic binder. The catalysts are then charged to reactors and sulfidedat 335 C., all as described with reference to the catalysts used formid-distillate hydrocracking, supra.

The temperature of operation is maintained at 335 C. and the pressure at1500 p.s.i. The sulfur-bearing feed is introduced to the reactors at arate of 1 v./v./hr. and hydrogen at a rate of 2000 to 3000 s.c.f./bbl.

The results of these runs are tabulated below.

TABLE xnr' Example No 48 49 50 51 52 53 Impregnated metals Co/M-...Co/Mo Mo Mo Mo Co/Mo. Chrysotile base 100% Mg 8% Al, 92% Mg.. Ni, 95% Mg100% N1... 100% N1..- 20% Al, 80% Mg. Surface area, mfi/tk; 147 160 86359. 392. Physical form otc ysotile Tubes.-. Tubes Tubes Tubes..."Flakes Flakes. Average 1 pore size of openings, A 11 2 11 180 22 85.Percent sulfur in product 1.29 1.17 1.20 1.06 1.12. Percent sulfurremoval 59-5 59 1 56.7.

1 Calculated by 4 (pore volume) /surface area.

HYDRODENITROGENATION 1000 s.c.f./bbl. to about 10,000 s.c.f./bbl., andpreferably from about 1000 s.c.f./bbl. to about 5000 s.c.f./bbl., and atsuperficial liquid hourly space velocities, LHSV, ranging from about 1to about 5, and preferably from about 1 to about 2. Temperaturesgenerally range from about 350 C. to about 390 C. at start-of-runconditions and from about 390 C. to about 430 C. at end-of-runconditions.

Chrysotiles are suitable for conducting hydrodenitrogenation processes,or processes for treating feedstocks containing organic nitrogencompounds, under conditions such 15 that the nitrogen content issignificantly reduced. Feedstocks which can be processed arenitrogen-bearing virgin and cracked stocks boiling above 180 C., typicalamong which are light and heavy cat cracker stocks, coker gas oils,middle distillates and virgin gas oils. Middle distillates EXAMPLES54-59 or heavy cat cycle stocks which can be processed are those Todemonstrate the hydrodenitrogenation process, a seboiling from about 220C. to about 340 C., or lighter ries of catalysts is prepared as in thoseruns demonstrated stocks boiling in the range of from about 220 C. toabout by reference to preceding Examples 48-53. These catalysts, 290 C.,gas oils boiling above about 340 C., e.g., light identified in the tableimmediately below, are employed gas oils boiling within the range offrom about 340 C. to process a nitrogen-bearing feed fed into thereactors to about 450 C., and heavy gas oils boiling within the at arate of l v./v./hr. with hydrogen at a rate of 2000 to range of fromabout 450 C. to about 540 C., and higher. 3000 s.c.f./bbl. of feed. A1500 p.s.i. pressure is main- Suitable hydrodenitrogenation catalystsare formed by tained in the reactors which are operated at 377 C.

compositing a chrysotile base and a hydrogenation compo- The results aretabulated below.

TABLE XIV Example No 54 55 5e 57 5s 59 Impregnated metals Chrysotilebase Surface area, rnfi/g Physical form of chrysotile P.p.m. nitrogen inproduct 300 363 262 9.6 36 51. Percent nitrogen removaL. 40.0. 27.4.47.6 98.1 92.8 89.9.

nent, particularly one selected from Group VI-B, VII-B REFORMING andVIII metals, or mixtures of these and other metals, 40 of the PeriodicTable of the Elements. Representative of The complex metal silicates arealso suitable for conthese metals are molybdenum, chromium, tungsten,rheducting reforming, or for use in a process wherein naphtha nium,iron, cobalt and nickel and metals of the platinum is catalyticallyconverted in an atmosphere rich in hydrogroup, e.g., platinum andpalladium, as well as combinagen to'upgra'de the'naphtha to products ofhigher octane. tions of these metals, their oxides, or sulfides.Particularly The principal reactions which occur in reforming arededesirable metal oxides are the oxides of nickel and cobalt,hydrogenation of naphthenes to form aromatics, dehydroand a particularlydesirable combination of such oxides is cyclization of parafiins to formaromatics, isomerization that of the oxides of nickel and molybdenum,such oxides of n-parafiins to form iso-paraffins and ring isomerization.being readily combinable with chrysotile as by impregna- Reforming isgenerally conducted at temperatures rangtion thereon. ing from about 400C. to about 550 C., and preferably The amount of the hydrogenationcomponent combined from about 150 p.s.i. to about 550 p.s.i., preferablyfrom with the chrysotile base can vary widely and will depend about 250p.s.i. to about 475 p.s.i. Hydrogen rates range on the feedstock as wellas on the particular nature of the generally from about 3000 s.c.f./bbl.to about 10,000 hydrogenation component. Generally, the amount of thes.c.f./bbl., and preferably from about 5000 s.c.f./bbl. to componentwill vary from about 0.1 to about 25 percent about 8000 s.c.f./bbl. andthe superficial liquid hourly by weight, based on the total weight ofthe composite. space linear velocity, LHSV, ranges from about 1 to aboutWhen a metal of the platinum series is employed, the 5, and preferablyfrom about 2 to about 4. amount will generally range from about 0.1 to 5percent. The feedstocks employed in these reactions are naph- Whenhydrogenation components such as the oxides and thas boiling within thegasoline range, suitably heavy sulfides of molybdenum, cobalt, tungsten,chromium, iron naphthas boiling in the range of from about 93-190 C. andnickel are employed, the amount will generally range or light naphthasboiling in the range of from about C from about 2 to 25 percent, andwhen the oxides of nickel 93 C. Naphthenic feeds are more easilyreformed, while and molybdenum are employed, the amount will rangeparafi'inic feeds are the more difiicult to reform. In selecgenerallyfrom about 1 to 5 percent, and 5 to 15 percent, tion of a suitablecatalyst, a chief consideration, thererespectively. A composite of about3 weight percent nickel fore, is to find a catalyst capable ofsynthesizing arooxide and 10 weight percent molybdenum oxide isparticmatics from paraffins and olefins, but particularly from ularlysuitable. naphthenes. The complex metal silicates of the presentParticularly preferred chrysotiles for use as bases ininvention can bereadily modified to produce such reformclude, e.g., magnesiumchrysotile, nickel chrysotile, coing activity. balt chrysotile and thevarious forms thereof wherein these I Catalysts found useful inreforming are composites metals are substituted by aluminum. formed froma chrysotile base and a hydrogenation com- Hydrodenitrogenationoperations are generally conductponent, the latter being deposited as byimpregnation upon ed at pressures ranging from about 500 p.s.i. to aboutthe base. Suitable bases are constituted of magnesium 2000 p.s.i., andpreferably from about 800 p.s.i. to about crysotile, nickel chrysotile,and mixed metal modifications 1500 p.s.i., at hydrogen gas rates rangingfrom about of these and other chrysotiles, particularly chrysotileswherein magnesium and nickel are particularly chrysotiles whereinmagnesium and nickel are partially replaced or substituted by aluminum.Suitable hydrogenation components, which can be incorporated into thechrysotile structure in original synthesis or deposited thereon as byimpregnation, are the Group VI-B, VII-B and VIII metals of the PeriodicTable of the Elements, preferred of which are the Group VIII platinumgroup metals, e.g., platinum, palladium and the like, or mixtures ofthese with other metals such as rhenium.

Suitably, the hydrogenation component, a metal or mixture of metals, isincorporated or added to the base in concentration ranging from about0.1 to about percent, based on the weight of the total catalyst, andpreferably in concentration ranging from about 0.3 to about 1 percent.In addition, the composite can contain from about 0.1 to about 1 percentof halogen, preferably chlorine or bromine.

EXAMPLES 60-65 To demonstrate the suitability of chrysotiles for use inthe formation of reforming catalysts, a series of chrysotiles of varyingcomposition are synthesized, dewatered, dried, identified by X-raydiffraction and ground to a fine powder.

According to a first technique, two catalysts are prepared for use inExamples 60-61, and a second technique is used to prepare the catalystsused in examples. In accordance with the first technique, a firstportion of the dry chrysotile powder is slurried in an aqueous solutionof tetra amine platinic chloride to exchange platinum onto the surfaceof the chrysotile. The second catalyst is similarly treated except thata small amount of platinum is added to the chrysotile base at the timeof synthesis, and the chrysotile then impregnated with an aqueoussolution of perrhenic acid to form a platinum-rhenium catalyst. Theimpregnated catalysts are filtered from the solution, dewatered bycentrifugation and dried for 16 hours at 105 C. in a vacuum.

The impregnated dried catlaysts are then mixed with 2 weight percent ofan organic binder, i.e., Sterotex, pilled, crushed to 14-35 mesh (Tylerseries) and then calcined in air at 510 C. to burn out the binder. Thecatalyst is then charged to reactors, stripped with nitrogen and thenreduced with hydrogen for one hour at 510 C. and 200 p.s.1.

In accordance with the second procedure, for preparation of catalystsfor use in Examples 62-65, the catalysts are prepared in generallysimilar manner except that a platinum impregnation is performed afterthe organic binder is burned from the catalyst. The portions of catalystare impregnated by admixing the aqueous solutions of chloroplatinic acidto the point of incipient wetness to effect the impregnation. Thecatalysts are then dried in air for 16 hours at 105 C., calcined in airat 510 C., charged to the reactors and then stripped with nitrogen, andthen reduced with hydrogen for one hour at 510 C. and 200 p.s.i.

A naphtha of 52 RON (clear) is then cut into the reactors at atemperature of 510 C. and at a feed rate of 4-7 w./hr./w. The runs areconducted for a period of 16 hours and a material balance is taken overthe period. Analysis is made of the product to determine RON (clear) aswell as the chlorine and carbon contents of the catalyst.

in an ionic-type reaction mechanism.

Typical of the feedstocks used in the alkylation process are iso-C -Cparaffins and gaseous C -C olefins, or aromatic hydrocarbons such asbenzene and substituted benzene, e.g., phenols and chlorobenzene, andgaseous and liquid C -C olefins. The alkylation process is conducted attemperatures ranging from about 20 C. to about 300 C., preferably attemperatures ranging from about 50 C. to about 100 C., at pressure ofatmospheric to about 1000 p.s.i., and preferably from about atmosphericto about 700 p.s.i.

Illustrative of catalysts which are useful in conducting alkylationreactions are magnesium chrysotile flakes, where part of the Mg isreplaced by aluminum.

Hydrodealkylation processes can also be conducted using the complexmetal silicates of this invention. A typical hydrodealkylation processis exemplified by removal of one or more alkyl groups from alkyl aryls,e.g., alkylbenzenes or alkyl naphthalenes, to produce high-grade benzeneor naphthalene as an end product. Benzene is mostly produced fromtoluene, although the alkylbenzenes can be dealkylated stepwise to yieldbenzene. Most naphthalene feedstocks contain substantial quantities ofalkylbenzenes, indanes, tetrahydronaphthalenes, indenes, biphenyl, andacetnaphthenes. The process is carried out in the presence of hydrogenwhich is consumed. Typical conditions to produce benzene include fromabout 540 to about 650 C., from about 500 to about 800 p.s.i., fromabout 5 to about 10 mol ratio of H to feed, and from about 0.25 to about2.5 w./hr./w. For naphthalene product, typical conditions are from about540 to about 650 C., from about 600 to about 800 p.s.i., from about 5 toabout 15 mol ratio of H to feed and from about 0.1 to about 2.5w./hr./w.

Typical of the catalysts that can be used for hydrodealkylation aremagnesium, nickel, and cobalt chrysotile flakes, particularly where partof the cation is substituted by aluminum. These chrysotile bases can beimpregnated by metals such as platinum, palladium, cobalt, molybdenum,chromium, nickel, or mixtures thereof.

These catalysts are also suitable for conducting polymerizationreactions, typical among which are those wherein low molecular weightgaseous and liquid olefins, including C -C olefins, are polymerized tolow molecular weight products boiling in the gasoline range and usefulas high octane number gasoline and petrochemical intermediates. Thepolymerization process is preferably carried out at temperatures rangingfrom about 0 to about 300 C., and preferably at temperatures rangingfrom about 20 C. to about 200 C. Pressures generally range fromatmospheric to about 3000 p.s.i., and preferably from atmospheric toabout 1500 p.s.i. Suitable space velocities range from about 1 v./v./hr.to about 10 v./v./

The results are given as tabulated below. hr., and preferably from about2 to about 4 v./v./hr.

TABLE XV Example No 00 01 02 63 e4 65 Im re nated metal Pt Re Pt" PtPt.. Pt. Chlhrfiie on catalyst Low Low High Hlgh High High. chrysotilebase 20% A1, Mg-.. 0.3% Pt, 99.7% Mg- 100% Mg 0.3% R8, 99.7% Mg-. 20%A1, 80% Mg--- IOK'EgCr, w im w-.. 4.0 6.9 4.0 4.0 4.0 4.0 Temp., Productoctane (RON clear)- Relative activity, percent l All flake material.

9 relative activity, activity of standard 0.3% Pt on A1203 reformingcatalyst (activity corrected for chlorine and carbon on catalyst).

Typical of the catalysts which can be used in polymerization reactionsare magnesium chrysotile flakes, when part of the magnesium is replacedby aluminum.

It is also apparent that various modifications and changes can be madein adaptation of these complex metal silicates, and chrysotiles, for usein hydrocarbon conversion reactions within the spirit and scope of thisinvention.

Among such modifications and changes:

Chrysotiles, e.g., can be treated or modified to improve their catalyticor adsorption properties in much the same manner as other catalyticmaterials. For example, the metallic cation population can be modifiedby base exchange, i.e., contact with an ionic solution of the cation tobe added to the chrysotile base. It is also known that contact withammonium salt solutions reduces the alkali metal cations by exchange. Ina similar manner the metal cations, including magnesium and aluminum,can be reduced by treatment with acids, the acid form of cation exchangeresins, or chelating agents. Conversely, the silica content of syntheticchrysotiles can be reduced by treating with strong caustic solutions, ifdesired.

Chrysotiles, e.g., can be dispersed in matrices of inorganic oxides suchas silica, alumina, combinations thereof or in naturally-occurringmaterials such as kaolin. The matrix material may be inert chemically orhave an activity which is complementary to the activity of thechrysotile. The matrix may serve the additional function of stabilizingthe chrysotile component to the environment of the reaction or of abinder to form the chrysotile to the appropriate particle size for theunit operation, for example, fluidizable solids or moving bed or fixedbed reactors.

Chrysotiles, e.g., may be rendered active for adsorption or catalysis bycalcination at temperatures below the point which produces substantialmodification of the crystal structure, i.e., for many syntheticchrysotile species about 650 C. In addition, chrysotiles can be renderedmore active for certain applications by modification in a steam orammonia atmosphere at elevated temperature. This also renders them moresusceptible to modification by subsequent cation exchange.

Chrysotiles, e.g., may be combined with active metals in high surfacearea form such as palladium, platinum, molybdenum, tungsten, nickel,cobalt and mixtures of these and other metals by exchange with solutionsof soluble salts of these and other metals, by precipitation ofinsoluble salts or hydroxides in the presence of synthetic chrysotiles.This may also be accomplished by adsorption of solutions of these metalseither as cations or complex anions followed by decomposition of thecomplex ion or evaporation of the solvent.

Chrysotiles, e.g., may be regenerated after use as adsorbent or catalystby stripping off adsorbed materials at high temperature with steam,ammonia, or inert gases. Nonvolatile but combustible residues may beremoved by stripping with an oxygen-containing gas which burns away theresidue.

These and other modifications will thus be apparent to those skilled inthe fuels processing and petrochemical arts.

Having described the invention, what is claimed is:

1. A process for the conversion of hydrocarbons comprising contactingsaid hydrocarbons at hydrocarbon conversion conditions with a layeredcomplex metal silicate composition characterized as having repeatingunits defined by the following structural formula:

where M and ii are monovalent and multivalent metal cations selectedfrom Groups I, II, III, IV-B, V-B, VI-B, VII-B and VIII of the PeriodicTable of the Elements, having an effective ionic radius ranging fromabout 0.5 to about 1 A., x is a number ranging from to 1 which expressesthe atomic fraction of the metals M and M, a

is the valence of M, b is the valence of if, n is a number equal invalue to that defined by the ratio w is a number ranging from 0 to 4,and the surface area of the composition ranges above m./ g.

2. The process of claim 1 wherein the effective ionic radius of themetal cations ranges from about 0.57 to about 0.91 A.

3. The process of claim 1 wherein the said composition contains at leasttwo metals.

4. The process of claim 1 wherein the composition is bimetallic.

5. The process of claim 4 wherein the metals are selected frommagnesium, nickel, cobalt, chromium, molybdenum, tungsten, palladium,platinum and aluminum.

6. The process of claim 1 wherein the said composition is in thephysical form of tubes, characterized as having walls of thicknessranging from about 30 A. to about 50 A., and internal openings ofdiameter ranging from about 60 A. to about A.

7. The process of claim 6 wherein the surface area of the compositionsranges to about 250 m. g.

8. The process of claim 1 wherein the said composition is in thephysical form of flakes, of thickness ranging from about 15 A. to about50 A.

9. The process of claim 1 wherein the surface area of the flakes rangesfrom about 250 A. to about 600 A., and higher.

10. The process of claim 1 wherein the said silicate composition has anX-ray powder diffraction pattern substantially the same as follows:

position is in the physical form of tubes.

12. The process of claim 1 wherein the silicate composition has an X-raypowder diffraction pattern substantially the same as follows:

d (A.): I 4.55 m.

13. The process of claim 12 wherein the silicate composition is in thephysical form of flakes.

14. A process for the conversion of hydrocarbons comprising contactingsaid hydrocarbons at hydrocarbon conversion conditions with a layeredcomplex metal silicate composition of surface area ranging above 110 m./g., and further characterized as having repeating units defined by thefollowing structural formula:

[(1-x)M +xM (OH) Si O -wH O where M and M are selected from monovalentand multivalent metal cations of Groups I, II, III, IV-B, V-B, VI-B,VII-B and VIII of the Periodic Table of the Elements, having aneffective ionic radius ranging from about 0.5 to about 1.0 A., x is anumber which expresses the atomic fraction of M and M and ranges from0.01 to 0.50, a is an expression for the valence of M and b is anexpression for the valence of M and is an integer ranging from 1 to 7, nis a number ranging from 2.5 to 3.3, and w is a number ranging from to4.

15. The process of claim 14 wherein at is a number ranging from 0.03 to0.2-0 and n is a number ranging from 2.7 to 3.0.

16. The process of claim 14 wherein the effective ionic radius of themetal cations ranges from about 0.57 to about 0.91 A.

17. The process of claim 14 wherein b is an integer ranging from 2 to 4.

18. The process of claim 14 wherein the composition is bimetallic.

19. The process of claim 15 wherein the metals are selected frommagnesium, nickel, cobalt, chromium, molybdenum, tungsten, palladium,platinum, and aluminum.

20. The process of claim 15 wherein the said composition is in thephysical form of tubes, characterized as having walls of thicknessranging from about 30 A. to about 50 A., and internal openings ofdiameter ranging from about 60 A. to about 150 A.

21. The process of claim wherein the surface area of the chrysotile isat least about 110 m. g.

22. The process of claim 21 wherein the surface area of the compositionsranges to about 250 m. g.

23. The process of claim 14 wherein the said composition is in thephysical form of flakes, of thickness ranging from about 15 A. to about50 A.

24. The process of claim 23 wherein the surface area of the flakesranges from about 250 A. to about 600 A. and higher.

25. The process of claim 14 wherein the said metal silicate compositionhas an X-ray powder diffraction pattern substantially the same asfollows:

position is in the physical form of tubes.

27. The process of claim 14 wherein the said silicate composition has anX-ray powder diffraction pattern substantially the same as follows:

d (A): I 4.55 m.

28. The process of claim 27 wherein the silicate composition is in thephysical form of flakes.

29. A process for the conversion of hydrocarbons comprising contactingsaid hydrocarbons at hydrocarbon conversion conditions with a crysotilehaving a surface area of at least 55 m. g.

30. The process of claim 29 wherein the surface area of the chrysotileranges at least 55 m. /g. to about 110 rn. g.

31. The process of claim 30 wherein the surface area of the chrysotileranges to about 250 m. g.

32. The process of claim 29 wherein the said chrysotile is in thephysical form of tubes, characterized as having walls of thicknessranging from about 30 A. to about 50 A., and internal openings ofdiameter ranging from about 60 A. to about 150 A.

33. The process of claim 29 wherein the said chrysotile composition hasan X-ray powder difiraction pattern substantially the same as follows:

d (A.): I 7.50 s. 4.50 m. 3.67 s.

d (A.): I 4.55 m.

38. The process of claim 37 wherein the chrysotile composition is in thephysical form of flakes.

39. A process for the conversion of hydrocarbons comprising contactingsaid hydrocarbons at hydrocarbon conversion conditions with a chrysotilehaving a surface area of at least 55 m. /g., said chrysotile having beenprepared from an aqueous reaction mixture containing silica, and a metalcation selected from Groups I, II, III, IV-B, V-B, VI-B, VIII-B and VIIIof the Periodic Table of the Elements, having an effective ionic radiusranging from about 0.5 to about 1.0 A.

40. The process of claim 39 wherein the effective ionic radius of themetal cations ranges from about 0.57 to about 0.91 A.

41. The process of claim 40 wherein the said chrysotile contains atleast two metals.

42. The process of claim 39 wherein the chrysotile is bimetallic.

43. The process of claim 42 wherein the metals are selected frommagnesium, nickel, cobalt, chromium, molybdenum, tungsten, palladium,platinum and aluminum.

44. The process of claim 39 wherein the said chrysotile is in thephysical form of tubes, characterized as having walls of thicknessranging from about 30 A. to about 50 A., and internal openings ofdiameter ranging from about 60 A. to about A.

45. The process of claim 39 wherein the said metal chrysotilecomposition has an X-ray powder diffraction pattern substantially thesame as follows:

d (A.): I 7.50 s. 4.50 m.

46. The process of claim 45 wherein the chrysotile composition is in thephysical form of tubes.

47. The process of claim 46 wherein the surface area of the chrysotileranges at least 55 m. /g. to about 110 mF/g.

48. The process of claim 46 wherein the surface area of the chrysotileranges to about 250 m. /g.

49. The process of claim 39 wherein the said composition is in thephysical form of flakes, of thickness ranging from about 15 A. to about50 A.

50. The process of claim 49 wherein the surface area of the flakesranges from about 250 A. to about 600 A. and higher.

51. The process of claim 39 wherein the chrysotile composition has anX-ray powder diffraction pattern substantially the same as follows:

52. The process of claim 49 wherein the chrysotile composition is in thephysical form of flakes.

53. The process of claim 1 wherein the surface area of the compositionranges above 110 m. /g., except where x=0, and M is nickel, the surfacearea of the composition ranges above about 125 m. /g., and where x=0,and M is cobalt, the surface area of the composition ranges above about190 mF/g.

54. A process for the hydrocracking of hydrocarbons to make naphtha andjet fuel comprising contacting said hydrocarbons, in the presence ofhydrogen, at temperatures ranging from about 250 C. to about 450 C., atpressures ranging from about 400 to about 3000 p.s.i., with a catalystcomposite comprising chrysotile having a surface area of at least 55 m./g., and a metallic hydrogenation component.

55. The process of claim 54 wherein the reaction is conducted attemperatures ranging from about 350 C. to about 425 C., and at pressuresranging from about 500 to about 2500 p.s.i.

56. The process of claim 54 wherein the hydrogenation component isselected from a group consisting of VI-B, VII-B, and VIII metals, of thePeriodic Table of the Elements, and mixtures thereof.

57. The process of claim 54 wherein the metal hydrogenation component isselected from platinum, palladium, tungsten, nickel, cobalt and thelike.

58. The process of claim 54 wherein the catalyst composites are mixedmetal chrysotiles selected from the group consisting of magnesiumaluminum chrysotile impregnated with a metal selected from palladium andplatinum, and mixtures of palladium and platinum; a magnesium-nickelchrysotile impregnated with a metal selected from moylbdenum andtungsten; magnesium-tungsten chrysotile impregnated with a metalselected from the group consisting of nickel and cobalt, and mixtures ofnickel and cobalt; magnesium-molybdenum chrysotile impregnated with ametal selected from the group consisting of nickel, cobalt, and mixturesof nickel and cobalt; nickel-tungsten chrysotile and cobalt-molybdenumchrysotile.

59. The process of claim 58 wherein the catalyst composites are employedin the presence of a compound selected from the group consistingessentially of organic sulfur, organic nitrogen, and mixtures thereof.

60. The process of claim 58 wherein the catalyst composites are employedin a sweet hydrocracking operation.

61. The process of claim 54 wherein the surface area of the chrysotileranges from at least 55 mfi/g. to at least 110 m.*/ g. of the chrysotileranges from about 110 mfi/g. to about 62. The process of claim 54wherein the surface area 36 of the chrysotile ranges from about 110mF/g. to about 250 mF/g.

63. The process of claim 54 wherein the said chrysotile is in thephysical form of tubes, characterized as having walls of thicknessranging from about 30 A. to about A., and internal openings of diameterranging from about 60 A. to about 150 A.

64. The process of claim 63 wherein the surface area of the compositionsranges to about 250 m. /g.

65. The process of claim 54 wherein the said composition is in thephysical form of flakes, of thickness ranging from about 15 A. to about50 A.

66. The process of claim 54 wherein the surface area of the flakesranges from about 250 A. to about 600 A. and higher.

67. The process of claim 54 wherein the said chrysotile has an X-raypowder diffraction pattern substantially the same as follows:

68. The process of claim 67 wherein the chrysotile is in the physicalform of tubes:

69. The process of claim 54 wherein the chrysotile has an X-ray powderdiffraction pattern substantially the same as follows:

d (A.): I 4.55 m.

70. The process of claim 69 wherein the chrysotile is in the physicalform of flakes.

71. A process for the hydrocracking of hydrocarbons to makemid-distillates comprising contacting said hydrocarbons, in the presenceof hydrogen, at temperatures ranging from about 370 C. to about 450 C.,at pressures ranging from about to about 3000 p.s.i., with a catalystcomposite comprising chrysotile having a surface area of at least 55 m./g., and a metallic hydrogenation component in the presence of organicsulfur and organic nitrogen.

72. The process of claim 71 wherein the chrysotile base is of acidityranging from about 0.2 to about 0.9, as measured by pyridine adsorption.

73. The process of claim 71 wherein the surface area of the chrysotileranges from at least 55 mP/g. to at least about m. /g.

74. The process of claim 71 wherein the surface area of the chrysotileranges from about 110 mF/g. to about 250 mP/g.

75. The process of claim 71 wherein the said chrysotile is in thephysical form of tubes, characterized as having walls of thicknessranging from about 30 A. to about 50 A., and internal openings ofdiameter ranging from about 60 A. to about A.

76. The process of claim 75 wherein the surface area of the chrysotileranges to about 250 mF/g.

77. The process of claim 71 wherein the said chrysotile composition isin the physical form of flakes, of thickness ranging from about 15 A. toabout 50 A.

37 78. The process of claim 71 wherein the surface area of the flakesranges from about 250 A. to about 600 A., and higher.

79. The process of claim 71 wherein the said chrysotile composition hasan X-ray powder diffraction pattern substantially the same as follows:

80. The process of claim 79 wherein the chrysotile composition is in thephysical form of tubes.

81. The process of claim 71 wherein the chrysotile composition has anX-ray powder difiraction pattern substantially the same as follows:

d (A.): I

4.55 m 3.22 w. 2.59 m. 1.73 w 1.54 m

82. The process of claim 81 wherein the chrysotile composition is in theform of flakes.

83. The process of claim 71 wherein the chrysotile is magnesiumchrysotile or nickel chrysotile.

84. The process of claim 83 wherein the chrysotile is magnesiumchrysotile, and from about 10 to about mole percent of the magnesium issubstituted by aluminum.

85. The process of claim 71 wherein the metallic hydrogenation componentis selected from Groups VI-B, VII-B and VIII metals.

86. The process of claim 85 wherein the metal hydrogenation component isselected from cobalt, molybdenum and mixtures thereof.

References Cited UNITED STATES PATENTS 1,681,238 8/1928 James 252-4511,698,009 1/ 1929 Weber 208-143 X 1,890,434 12/ 1932 Krauch et al 208-10DELBERT E. GANTZ, Primary Examiner G. E. SCHMITKONS, Assistant ExaminerUS. Cl. X.R.

